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Abstract:

This invention relates to a composition, comprising: an unsaturated
functionalized monomer of from about 5 to about 30 carbon atoms, which
is: (a) polymerized to form a functionalized polymer; (b) copolymerized
with a comonomer to form a functionalized copolymer; or (c) reacted with
an enophilic reagent to form a polyfunctionalized monomer. The
polyfunctionalized monomer may be polymerized to form a
polyfunctionalized polymer which may be further reacted with one or more
additional reagents. The invention relates to lubricants, functional
fluids, fuels, dispersants, detergents and polymeric resins.

Claims:

1. A composition, comprising: a functionalized monomer comprising a
hydrocarbyl group with one or more carbon-carbon double bonds and one or
more functional groups attached to the hydrocarbyl group, the hydrocarbyl
group containing from about 5 to about 30 carbon atoms, or from about 6
to about 30 carbon atoms, or from about 8 to about 30 carbon atoms, or
from about 10 to about 30 carbon atoms, or from about 12 to about 30
carbon atoms, or from about 14 to about 30 carbon atoms, or from about 16
to about 30 carbon atoms, or from about 5 to about 18 carbon atoms, or
from about 12 to about 18 carbon atoms, or about 18 carbon atoms, the
functional group comprising a carboxylic acid group or a derivative
thereof, a hydroxyl group, an amino group, a carbonyl group, a cyano
group, or a mixture of two or more thereof, wherein the functionalized
monomer is: (a) polymerized to form a functionalized polymer; (b)
copolymerized with a comonomer to form a functionalized copolymer; or (c)
reacted with an enophilic reagent to form a polyfunctionalized monomer,
the enophilic reagent comprising an oxidizing agent, a sulfurizing agent,
a sulfonating agent, an enophilic acid reagent, an aromatic compound, a
hydroxylating agent, a halogenating agent, or a mixture of two or more
thereof, the enophilic reagent being reactive towards one or more of the
carbon-carbon double bonds in the hydrocarbyl group.

2. The composition of claim 1 wherein the functionalized monomer
comprises an unsaturated carboxylic acid, anhydride, ester, amide, imide,
alcohol, amine, aldehyde, ketone, nitrile, or a mixture of two or more
thereof.

3. The composition of claim 1 wherein the functionalized polymer
comprises a homopolymer.

4. The composition of claim 1 wherein the functionalized polymer
comprises a copolymer containing repeating units derived from two or more
of the functionalized monomers.

5. The composition of claim 1 wherein the functionalized copolymer
comprises from about 5 to about 99 mole percent, or from about 5 to about
70 mole percent, or from about 5 to about 50 mole percent, or from about
5 to about 30 mole percent, repeating units derived from the
functionalized monomer.

6. The composition of claim 1 wherein the functionalized polymer and/or
functionalized copolymer comprises one or more carbon-carbon double bonds
and is reacted with an enophilic reagent to form a polyfunctionalized
polymer and/or polyfunctionalized copolymer, the enophilic reagent
comprising an oxidizing agent, a sulfurizing agent, a sulfonating agent,
an enophilic acid reagent, an aromatic compound, a hydroxylating agent, a
halogenating agent, or a mixture of two or more thereof, the enophilic
reagent being reactive toward one or more of the carbon-carbon double
bonds in the functionalized polymer and/or functionalized copolymer.

7. The composition of claim 1 wherein the polyfunctionalized monomer is
polymerized to form a polyfunctionalized polymer.

8. The composition of claim 1 wherein the polyfunctionalized monomer is
copolymerized with a comonomer to form a polyfunctionalized copolymer.

10. The composition of any of the preceding claims wherein the comonomer
comprises an olefin containing from 2 to about 30, or from about 6 to
about 24, carbon atoms per molecule.

11. The composition of any of the preceding claims wherein the
hydrocarbyl group contains one, two, three or four carbon-carbon double
bonds.

12. The composition of any of the preceding claims wherein the comonomer
contains one, two, three or four carbon-carbon double bonds.

13. The composition of any of claims 1 to 5 or 9 to 12 wherein the
functionalized polymer and/or functionalized copolymer has a number
average molecular weight in the range from about 300 to about 50,000, or
from about 300 to about 20,000, or from about 300 to about 10,000, or
from about 300 to about 5,000, or from about 500 to about 3000.

14. The composition of any of claims 6 to 12 wherein the
polyfunctionalized polymer and/or polyfunctionalized copolymer has a
number average molecular weight in the range from about 300 to about
50,000, or from about 300 to about 20,000, or from about 300 to about
10,000, or from about 300 to about 5,000, or from about 500 to about
3000.

15. The composition of any of the preceding claims wherein the
functionalized monomer contains a carbon-carbon double bond in the
terminal position of the hydrocarbyl group.

16. The composition of any of the preceding claims wherein the comonomer
comprises an olefin chain with a carbon-carbon double bond in the
terminal position of the olefin chain.

17. The composition of any of the preceding claims wherein the functional
group is attached to a terminal carbon atom on the hydrocarbyl group.

18. The composition of any of the preceding claims wherein the functional
group is attached to an internal carbon atom in the hydrocarbyl group.

19. The composition of any of the preceding claims wherein the oxidizing
agent comprises a compound containing an oxygen-oxygen single bond.

20. The composition of any of the preceding claims wherein the oxidizing
agent comprises a compound containing a peroxide group or a peroxide ion.

21. The composition of any of the preceding claims wherein the oxidizing
agent comprises hydrogen peroxide, an organic peroxide, an inorganic
peroxide, or a mixture of two or more thereof.

22. The composition of any of the preceding claims wherein the
sulfurizing agent comprises elemental sulfur, sulfur halide, a
combination of sulfur or sulfur oxide with hydrogen sulfide, phosphorus
sulfide, aromatic sulfide, alkyl sulfide, sulfurized olefin, sulfurized
oil, sulfurized fatty ester, diester sulfide, or a mixture of two or more
thereof.

23. The composition of any of the preceding claims wherein the
sulfonating agent comprises sulfur trioxide, oleum, chlorosulfonic acid,
sodium bisulfite, or a mixture of two or more thereof.

24. The composition of any of the preceding claims wherein the enophilic
acid reagent comprises one or more alpha-beta olefinically unsaturated
carboxylic acids and/or derivatives thereof.

25. The composition of any of the preceding claims wherein the enophilic
acid reagent comprises one or more compounds represented by the formula
##STR00034## wherein R1 and R2 are independently hydrogen or
hydrocarbyl groups.

26. The composition of any of the preceding claims wherein the enophilic
acid reagent comprises one or more alpha, beta unsaturated dicarboxylic
acids and/or derivatives thereof.

28. The composition of any of the preceding claims wherein the aromatic
compound comprises an aromatic compound, aliphatic-substituted aromatic
compound, or aromatic-substituted aliphatic compound.

29. The composition of any of the preceding claims wherein the aromatic
compound comprises a substituted aromatic compound containing one or more
substituent groups selected from hydroxy, halo, nitro, amino, cyano,
alkoxy, acyl, epoxy, acryloxy, mercapto, or a mixture of two or more
thereof.

30. The composition of any of the preceding claims wherein the aromatic
compound contains from 6 to about 40 carbon atoms.

32. The composition of any of the preceding claims wherein the aromatic
compound comprises o-, m- and/or p-xylene, toluene, tolylaldehyde,
aminotoluene, o-, m- and/or p-cresol, benzaldehyde, or a mixture of two
or more thereof.

33. The composition of any of the preceding claims wherein the
hydroxylating agent comprises water, hydrogen peroxide, or a mixture
thereof.

35. A dispersant comprising the reaction product of a nitrogen-containing
reagent or an oxygen-containing reagent, with: (i) a functionalized
monomer comprising a hydrocarbyl group with one or more carbon-carbon
double bonds and one or more functional groups attached to the
hydrocarbyl group, the hydrocarbyl group containing from about 5 to about
30 carbon atoms, or from about 6 to about 30 carbon atoms, or from about
8 to about 30 carbon atoms, or from about 10 to about 30 carbon atoms, or
from about 12 to about 30 carbon atoms, or from about 14 to about 30
carbon atoms, or from about 16 to about 30 carbon atoms, or from about 5
to about 18 carbon atoms, or from about 12 to about 18 carbon atoms, or
about 18 carbon atoms, the functional group comprising a carboxylic acid
or derivative thereof; (ii) a polymer derived from one or more of the
functionalized monomers (i); (iii) a copolymer derived from one or more
of the functionalized monomers (i) and one or more olefin comonomers;
(iv) the reaction product of an enophilic acid reagent with the monomer
(i), polymer (ii) and/or copolymer (iii); or (v) a mixture of two or more
of (i), (ii), (iii) and (iv).

36. The dispersant of claim 35 wherein the olefin comonomer contains from
2 to about 30 carbon atoms, or from about 6 to about 24 carbon atoms.

38. The dispersant of claim 35 or claim 36 wherein the enophilic acid
reagent comprises one or more compounds represented by the formula
##STR00035## wherein R1 and R2 are independently hydrogen or
hydrocarbyl groups.

41. The dispersant of any of claims 35 to 40 wherein the copolymer (iii)
contains from about 5 to about 99 mole percent, or from about 5 to about
70 mole percent, or from about 5 to about 50 mole percent, or from about
5 to about 30 mole percent, of repeating units derived from the
functionalized monomer.

42. The dispersant of any of claims 35 to 41 wherein the
nitrogen-containing reagent comprises ammonia, an amine containing one or
more primary and/or secondary amino groups, a mono-substituted amine,
di-substituted amine, an amino-alcohol, or a mixture of two or more
thereof.

44. The dispersant of any of claims 35 to 41 wherein the
nitrogen-containing reagent comprises a polyamine represented by the
formula ##STR00036## wherein each R is independently hydrogen, a
hydrocarbyl group or a hydroxy-substituted hydrocarbyl group containing
up to about 30 carbon atoms, or up to about 10 carbon atoms, with the
proviso that at least one R is hydrogen, n is a number in the range from
1 to about 10, or from about 2 to about 8, and R1 is an alkyene
group containing 1 to about 18 carbon atoms, or 1 to about 10 carbon
atoms, or from about 2 to about 6 carbon atoms.

47. The dispersant of any of claims 35 to 41 wherein the
oxygen-containing reagent comprises one or more polyols containing from 2
to about 10 carbon atoms, and from 2 to about 6 hydroxyl groups.

48. The dispersant of any of claims 35 to 41 wherein the
oxygen-containing reagent comprises ethylene glycol, glycerol,
trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,
1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,
2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,
2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, or a mixture
of two or more thereof.

49. The dispersant of any of claims 35 to 41 wherein the dispersant is
derived from an oxygen-containing reagent, the dispersant being formed by
the reaction of the monomer (i), polymer (ii), copolymer (iii) and/or
reaction product (iv) with the oxygen-containing reagent to form an
intermediate product, the intermediate product being reacted with an
amine.

50. The dispersant of claim 49 wherein the amine comprises a monoamine,
diamine, polyamine, polyalkyene polyamine, or a mixture of two or more
thereof.

51. The dispersant of any of claims 35 to 50, wherein the dispersant is
mixed with a succinimide.

52. A detergent comprising a neutral or overbased material derived from a
metal or metal compound, and: (i) a functionalized monomer comprising a
hydrocarbyl group with one or more carbon-carbon double bonds and one or
more functional groups attached to the hydrocarbyl group, the hydrocarbyl
group containing from about 5 to about 30 carbon atoms, or from about 6
to about 30 carbon atoms, or from about 8 to about 30 carbon atoms, or
from about 10 to about 30 carbon atoms, or from about 12 to about 30
carbon atoms, or from about 14 to about 30 carbon atoms, or from about 16
to about 30 carbon atoms, or from about 5 to about 18 carbon atoms, or
from about 12 to about 18 carbon atoms, or about 18 carbon atoms, the
functional group comprising a carboxylic acid group or derivative
thereof; (ii) a polymer derived from one or more of the functionalized
monomers (i); (iii) a copolymer derived from one or more of the
functionalized monomers (i) and one or more olefin comonomers; (iv) the
reaction product of an enophilic acid reagent with the monomer (i),
polymer (ii) and/or copolymer (iii); or (v) a mixture of two or more of
(i), (ii), (iii) and (iv).

53. The detergent of claim 52 wherein the olefin comonomer contains from
2 to about 30 carbon atoms, or from about 6 to about 24 carbon atoms.

56. The detergent of any of claims 52 to 55 wherein the copolymer (iii)
contains from about 5 to about 99 mole percent, or from about 5 to about
70 mole percent, or from about 5 to about 50 mole percent, or from about
6 to about 70 mole percent, of repeating units derived from the
functionalized monomer.

57. The detergent of any of claims 52 to 56 wherein the metal comprises
an alkali metal, alkaline earth metal, titanium, zirconium, molybdenum,
iron, copper, aluminum, zinc, or a mixture of two or more thereof.

58. The detergent of any of claims 52 to 57 wherein one or more
alkylbenzenesulfonic acids are mixed with the functionalized monomer (i),
polymer (ii), copolymer (iii) and/or reaction product (iv).

59. The detergent of any of claims 52 to 58 wherein the detergent is
derived from (1) the functionalized monomer (i), polymer (ii), copolymer
(iii), reaction product (iv), or mixture (v), optionally, in combination
with an alkaryl sulfonic acid, and (2) a reaction medium, (3) a
stoichiometric excess of at least one metal base, (4) a promoter, and (5)
an acidic material.

60. The detergent of any of claims 52 to 59 wherein the detergent
comprises a boron-containing overbased material.

61. A concentrate composition comprising from about 0.1% to about 99% by
weight, or from about 10% to about 90% by weight, of the composition of
any of claims 1 to 34, dispersant of any of claims 35 to 51, detergent of
any of claims 52 to 60, and a normally liquid diluent.

62. A lubricant or functional fluid composition, comprising a base oil,
the base oil comprising a polymer derived from one or more functionalized
monomers, the functionalized monomer comprising a hydrocarbyl group with
one or more carbon-carbon double bonds and one or more functional groups
attached to the hydrocarbyl group, the hydrocarbyl group containing from
about 5 to about 30 carbon atoms, or from about 6 to about 30 carbon
atoms, or from about 8 to about 30 carbon atoms, or from about 10 to
about 30 carbon atoms, or from about 12 to about 30 carbon atoms, or from
about 14 to about 30 carbon atoms, or from about 16 to about 30 carbon
atoms, or from about 5 to about 18 carbon atoms, or from about 12 to
about 18 carbon atoms, or about 18 carbon atoms, the functional group
comprising a carboxylic acid group or a derivative thereof, the polymer
having a number average molecular in the range of about 300 to about
50,000 or from about 300 to about 20,000.

63. The lubricant or functional fluid of claim 62 wherein the base oil is
blended with an API Group I, Group II, Group III, Group IV, Group V base
oil and/or a biologically derived oil.

64. The lubricant or functional fluid of claim 62 or claim 63 wherein the
lubricant of functional fluid comprises a fill-for-life fluid.

65. A lubricant or functional fluid composition, comprising a base oil,
the base oil comprising a copolymer derived from a functionalized monomer
and an olefin comonomer, the functionalized monomer comprising a
hydrocarbyl group with one or more carbon-carbon double bonds and one or
more functional groups attached to the hydrocarbyl group, the hydrocarbyl
group containing from about 5 to about 30 carbon atoms, or from about 6
to about 30 carbon atoms, or from about 8 to about 30 carbon atoms, or
from about 10 to about 30 carbon atoms, or from about 12 to about 30
carbon atoms, or from about 14 to about 30 carbon atoms, or from about 16
to about 30 carbon atoms, or from about 5 to about 18 carbon atoms, or
from about 12 to about 18 carbon atoms, or about 18 carbon atoms, the
functional group comprising a carboxylic acid group or a derivative
thereof, a hydroxyl group, an amino group, a carbonyl group, a cyano
group, or a mixture of two or more thereof, the copolymer containing from
about 5 to about 30 mole percent, or from about 10 to about 25 mole
percent repeating units derived from the functionalized monomer, the
copolymer have a number average molecular weight in the range of about
300 to about 50,000, or from about 300 to about 20,000.

66. The lubricant or functional fluid of claim 64 wherein the base oil is
blended with an API Group I, Group II, Group III and/or Group IV base
oil.

67. The lubricant or functional fluid of claim 65 or claim 66 wherein the
lubricant or functional fluid comprises an engine oil or a drive line
fluid.

68. A lubricant or functional fluid comprising the dispersant of any of
claims 35 to 51.

69. A lubricant or functional fluid comprising the detergent of any of
claims 52 to 60.

71. The lubricant or functional fluid of any of claims 62 to 70 wherein
the lubricant or functional fluid composition comprises a grease
composition, the grease composition comprising lithium hydroxide, lithium
hydroxide monohydrate, or a mixture thereof.

72. A fuel composition, comprising a normally liquid fuel and the
dispersant of any of claims 35 to 51.

73. The fuel composition of claim 72 wherein the normally liquid fuel is
derived from petroleum, crude oil, a Fischer-Tropsch process, coal,
natural gas, oil shale, biomass, or a mixture of two or more thereof.

78. The composition of any of the preceding claims wherein the
functionalized monomer comprises a natural oil derived unsaturated fatty
acid, unsaturated fatty ester, polyunsaturated fatty acid,
polyunsaturated fatty ester, or a mixture of two or more thereof.

79. The composition of any of the preceding claims wherein the
functionalized monomer comprises a natural oil derived unsaturated
monoglyceride, unsaturated diglyceride, unsaturated triglyceride, or a
mixture of two or more thereof.

80. The composition of any of the preceding claims wherein the
functionalized monomer comprises: an alkene chain of about 10 to about 30
carbon atoms and a carbon-carbon double bond between the C9 and
C10 carbon atoms in the alkene chain; or an alkene chain of about 8
to about 30 carbon atoms and a carbon-carbon double bond between the
C6 and C7 carbon atoms in the alkene chain; or an alkene chain
of about 12 to about 30 carbon atoms and a carbon-carbon double bond
between the C11 and C12 carbon atoms in the alkene chain; or an
alkene chain of about 14 to about 30 carbon atoms and a carbon-carbon
double bond between the C13 and C14 carbon atoms in the alkene
chain; or an alkene chain of about 14 to about 30 carbon atoms and
carbon-carbon double bonds between the C9 and C10 carbon atoms
and between the C12 and C13 carbon atoms in the alkene chain;
or an alkene chain of about 16 to about 30 carbon atoms and carbon-carbon
double bonds between the C9 and C10 carbon atoms, between the
C12 and C13 carbon atoms, and between C15 and C16
carbon atoms in the alkene chain; or an alkene chain of about 16 to about
30 carbon atoms and carbon-carbon double bonds between the C6 and
C7 carbon atoms, between the C9 and C10 carbon atoms,
between the C12 and C13 carbon atoms, and between the C15
and C16 carbon atoms in the alkene chain.

81. The composition of any of the preceding claims wherein the
functionalized monomer is derived from a natural oil, the natural oil
comprising vegetable oil, algae oil, fungus oil, animal oil or fat, tall
oil, or a mixture of two or more thereof.

85. The composition of any of the preceding claims wherein the
functionalized monomer is derived from a metathesized natural oil, the
metathesized natural oil comprising the product of a self-metathesis
process or a cross-metathesis process.

86. The composition of claim 85 wherein the metathesized natural oil is
made by reacting one or more natural oils and/or natural oil derived
unsaturated carboxylic acids and/or esters in the presence of a
metathesis catalyst to form the metathesized natural oil.

87. The composition of claim 85 wherein the metathesized natural oil is
made by reacting (a) one or more natural oils and/or natural oil derived
unsaturated carboxylic acids and/or esters with (b) another olefinic
compound in the presence of a metathesis catalyst.

88. The composition of claim 85 wherein the metathesized natural oil is
made by reacting a natural oil and/or natural oil derived unsaturated
carboxylic acid and/or ester in the presence of a metathesis catalyst to
form a first metathesized natural oil; and then reacting the first
metathesized natural oil in a self-metathesis reaction to form another
metathesized natural oil, or reacting the first metathesized natural oil
in a cross-metathesis reaction with a natural oil and/or natural oil
derived unsaturated carboxylic acid and/or ester to form another
metathesized natural oil.

89. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst comprising a metal carbene catalyst based upon
ruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten.

90. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by the following formula (I)
##STR00037## wherein: M is ruthenium, molybdenum, osmium, chromium,
rhenium, and/or tungsten; L1, L2 and L3 are neutral
electron donor ligands; n is 0 or 1, such that L3 may or may not be
present; m is 0, 1, or 2; X1 and X2 are anionic ligands; and
R1 and R2 are independently selected from hydrogen,
hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, and functional groups,
wherein any two or more of X1, X2, L1, L2, L3,
R1, and R2 can be taken together to form a cyclic group, and
further wherein any one or more of X1, X2, L1, L2,
L3, R1, and R2 may be attached to a support.

91. The composition of claim 90 wherein M is Ru, W and/or Mo.

92. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by the formula ##STR00038##
wherein: M is a Group 8 transition metal; L1, L2 and L3
are neutral electron donor ligands; n is 0 or 1, such that L3 may or
may not be present; m is 0, 1, or 2; X1 and X2 are anionic
ligands; and R1 and R2 are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing
hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and
functional groups, wherein any two or more of X1, X2, L1,
L2, L3, R1, and R2 can be taken together to form a
cyclic group, and further wherein any one or more of X1, X2,
L1, L2, L3, R1, and R2 may be attached to a
support; X and Y are independently N, O, S, or P; p is zero when X is O
or S; q is zero when Y is O or S; p is 1 when X is N or P; q is 1 when Y
is N or P; and Q1, Q2, Q3 and Q4 are independently
linkers, and w, x, y and z are independently zero or 1.

93. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by one or more of the following
formulae ##STR00039## wherein: L1 is a neutral electron donor
ligand; X1 and X2 are independently anionic ligands; and M is a
Group 8 transition metal.

94. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by one or more of the following
formulae (VII), (VIII), (IX) or (X): ##STR00040## wherein: M is a Group
8 transition metal; L1, L2 and L3 are neutral electron
donor ligands; r and s are independently zero or 1; t is an integer in
the range from zero to 5; X1 and X2 are anionic ligands; and
R1 and R2 are independently selected from hydrogen,
hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, and functional groups,
wherein any two or more of X1, X2, L1, L2, L3,
R1, and R2 can be taken together to form a cyclic group, and
further wherein any one or more of X1, X2, L1, L2,
L3, R1, and R2 may be attached to a support; Y is a
non-coordinating anion; Z1 and Z2 are independently selected
from --O--, --S--, --NR2--, --PR2--, --P(═O)R2--,
--P(OR2)--, --P(═O)(OR2)--, --C(═O)--, --C(═O)O--,
--OC(═O)--, --OC(═O)O--, --S(═O)--, and --S(═O)2--;
and Z3 is a cationic moiety.

95. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by the formula ##STR00041##
wherein: X1 and X2 are anionic ligands; L1 is a neutral
electron donor ligand; R1 is selected from hydrogen, hydrocarbyl,
substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; Y is a
positively charged Group 15 or Group 16 element substituted with
hydrogen, C1-C12 hydrocarbyl, substituted C1-C12
hydrocarbyl; heteroatom-containing C1-C12 hydrocarbyl, or
substituted heteroatom-containing hydrocarbyl; and Z.sup.- is a
negatively charged counterion.

97. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by structures 12, 14 or 16, where
Ph is phenyl, Mes is mesityl, and Cy is cyclohexyl: ##STR00042##

98. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by structures 18, 20, 22, 24, 26 or
28 where Ph is phenyl, Mes is mesityl, py is pyridyl, Cp is cyclopentyl
and Cy is cyclohexyl: ##STR00043##

99. The composition of any of claims 85 to 88 wherein the metathesized
natural oil is formed in the presence of a metathesis catalyst, the
metathesis catalyst being represented by one or more of the following
structures ##STR00044## ##STR00045## ##STR00046## ##STR00047##
wherein Ph represents phenyl, Cy represents cyclohexane, Me represents
methyl, nBu represents n-butyl, i-Pr represents isopropyl, py represents
pyridine (coordinated through the N atom), and Mes represents mesityl
(i.e., 2,4,6-trimethylphenyl).

100. The composition of any of claims 85 to 99 wherein the natural oil or
natural oil derived unsaturated carboxylic acid, salt and/or ester is at
least partially hydrogenated prior to the reaction in the presence of the
metathesis catalyst.

101. The composition of any of claims 85 to 100 wherein the metathesized
natural oil comprises from 1 to about 100, or from 2 to about 50, or from
2 to about 30, or from 2 to about 10 metathesis repeating groups.

102. The composition of any of claims 85 to 101 wherein the metathesized
natural oil comprises a metathesis dimer, metathesis trimer, metathesis
tetramer, metathesis pentamer, metathesis hexamer, metathesis heptamer,
metathesis octamer, metathesis nonamer, metathesis decamer, or a mixture
of two or more thereof.

[0002] This invention relates to functionalized monomers and polymers, and
to lubricants, functional fluids, fuels, dispersants and detergents, and
polymeric resins or plastics for molded or extruded articles, adhesives,
coatings, and the like.

BACKGROUND

[0003] Monomers commonly used in the preparation of polymers are often
mono-functional in nature, which limits potential uses for derivatives.

SUMMARY

[0004] The functionalized monomers of the present invention may be
difunctional or polyfunctional. These monomers offer flexibility as well
as means to prepare novel polymers and copolymers with utility in a wide
breadth of applications. These monomers may undergo high degrees of
polymerization, resulting in polymers of unique molecular weight
distributions and structural shapes, some of which may have use as
specialty polymers to be employed in new applications. The term "polymer"
is used herein to refer to homopolymers and/or copolymers, unless
indicated otherwise.

[0005] The functionalized monomers of the present invention may be
polymerized to yield polymers with unique properties that are easy to
process and are bio-compatible. These polymers may have utility in many
applications and products, such as lubricants, functional fluids, fuels,
molded or extruded articles, pharmaceuticals, cosmetics, personal care
products, adhesives, coatings, and the like. The monomers and polymers
may be used as base oils for lubricants and functional fluids, and for
providing functional additives for lubricants, functional fluids and
fuels. This may provide for an advantageous balance between various
performance characteristics while selecting suitable monomers and
polymers that are compatible with acceptable manufacturing techniques.

[0006] The functionalized monomer may be derived from a natural oil or a
metathesized natural oil. The natural oils and metathesized natural oils
employed herein may provide the advantage of comprising or being derived
from renewable sources (e.g., vegetable oils, animal fats or oils, and
the like) and may be obtained using environmentally friendly production
techniques with less energy than conventional processes for making
lubricants, functional fluids, fuels, functional additives, polymeric
resins, and the like, derived from petroleum. This technology may be
referred to as "green" technology.

[0007] Synthetic lubricants are commonly used in passenger car motor oils,
heavy-duty diesel engine oils, marine and railroad engine lubricants,
automatic transmission fluids, hydraulic fluids, gear oils, and
industrial lubricants, such as metalworking fluids and lubricating
greases. The purpose of these oils is to provide improved friction and
wear control, rapid dissipation of heat, and the dissolution of and/or
facilitating the removal of service-related contaminants. Achieving a
proper balance between various performance characteristics is an
important consideration in selecting a synthetic lubricant for a
particular application. For example, polyolefin based lubricants
typically exhibit good low-temperature properties, high viscosity index,
and excellent thermal stability, but poor solvency. As a result, these
lubricants tend to be inadequate without the presence of additional polar
base stock-containing components. Conversely, polar base stock-containing
lubricants, such as those based on synthetic esters and vegetable oils,
typically exhibit good solvency and high surface affinity. However, these
lubricants tend to be inadequate with respect to resistance to wear. The
problem, therefore, is to provide a synthetic lubricant that exhibits
both good solvency and good resistance to wear reduction characteristics.
This invention provides a solution to this problem.

[0008] Ashless dispersants are additives used in lubricants, functional
fluids and fuels to prevent oxidation-derived deposits from impairing
function. Lubricants, functional fluids and fuels that employ these
additives include passenger car motor oils, heavy-duty diesel engine
oils, marine and railroad engine lubricants, automatic transmission
fluids, gear oils, and the like, with the largest use typically being in
automotive and industrial engine oils. The amount of dispersant used in a
lubricant or functional fluid depends upon the specific application but,
typically, constitutes from about 0.1 percent to about 30 percent by
weight of the lubricant or functional fluid. In fuels, the amount of
dispersant is typically less than in lubricants or functional fluids. The
problem is to provide a dispersant having improved tendencies for
suspending the by-products of combustion (e.g., soot) and lubricant or
functional fluid degradation (e.g., resin, varnish, lacquer and carbon
deposits) in order to keep equipment surfaces and passageways clean. This
invention provides a solution to this problem.

[0009] Detergents (e.g., metal-containing detergents that form ash upon
combustion) are used as additives in lubricants and functional fluids to
prevent oxidation-derived deposits from separating on surfaces and
impairing function. Lubricants and functional fluids that typically
employ these additives include passenger car motor oils, heavy-duty
diesel engine oils, marine and railroad engine lubricants, and to a
lesser degree automatic transmission fluids, gear oils, and the like,
with the largest use typically being in automotive and industrial engine
oils. The amount of detergent used in a lubricant or functional fluid
depends upon the specific application but, typically, constitutes from
about 0.1 percent to about 35 percent by weight of the lubricant or
functional fluid. The problem is to provide detergents having improved
tendencies for neutralizing acidic combustion and fuel oxidation-derived
deposit precursors, and for suspending these by-products and their
resultant salts in oil, thereby controlling corrosion and reducing the
formation of surface deposits. This invention provides a solution to this
problem.

[0010] This invention relates to a composition, comprising: a
functionalized monomer comprising a hydrocarbyl group with one or more
carbon-carbon double bonds and one or more functional groups attached to
the hydrocarbyl group, the hydrocarbyl group containing from about 5 to
about 30 carbon atoms, or from about 6 to about 30 carbon atoms, or from
about 8 to about 30 carbon atoms, or from about 10 to about 30 carbon
atoms, or from about 12 to about 30 carbon atoms, or from about 14 to
about 30 carbon atoms, or from about 16 to about 30 carbon atoms, or from
about 5 to about 18 carbon atoms, or from about 12 to about 18 carbon
atoms, or about 18 carbon atoms, the functional group comprising a
carboxylic acid group or a derivative thereof, a hydroxyl group, an amino
group, a carbonyl group, a cyano group, or a mixture of two or more
thereof, wherein the functionalized monomer is: (a) polymerized to form a
functionalized polymer; (b) copolymerized with a comonomer to form a
functionalized copolymer; or (c) reacted with an enophilic reagent to
form a polyfunctionalized monomer, the enophilic reagent comprising an
oxidizing agent, a sulfurizing agent, a sulfonating agent, an enophilic
acid reagent, an aromatic compound, a hydroxylating agent, a halogenating
agent, or a mixture of two or more thereof, the enophilic reagent being
reactive towards one or more of the carbon-carbon double bonds in the
hydrocarbyl group. The reaction with the enophilic reagent provides the
functionalized monomer with additional levels of functionality, the
monomer with such additional levels of functionality sometimes being
referred to herein as a polyfunctional monomer.

[0011] The functionalized monomer may comprise an unsaturated carboxylic
acid, anhydride, ester, amide, imide, alcohol, amine, aldehyde, ketone,
nitrile, or a mixture of two or more thereof.

[0012] The functionalized monomer may comprise one or more carbon-carbon
double bonds. One of these double bonds may be in a terminal position of
the hydrocarbyl group. The functional group may be attached to a terminal
carbon atom on the hydrocarbyl group or to an internal carbon atom in the
hydrocarbyl group.

[0014] The olefin comonomer may contain from 2 to about 30, or from about
6 to about 24, carbon atoms per molecule. The olefin comonomer may be a
monoene, diene, triene, tetraene, or mixture of two or more thereof.

[0015] The functionalized polymer may comprise a homopolymer containing
repeating units derived from the functionalized monomer, or a copolymer
containing repeating units derived from two or more of the functionalized
monomers.

[0016] The functionalized copolymer may comprise from about 5 to about 99
mole percent, or from about 5 to about 70 mole percent, or from about 5
to about 50 mole percent, or from about 5 to about 30 mole percent
repeating units, derived from one or more of the functionalized monomers,
the remainder of the copolymer comprising one or more of the
above-indicated comonomers.

[0017] The functionalized polymer and/or functionalized copolymer may have
a number average molecular weight in the range from about 300 to about
50,000, or from about 300 to about 20,000, or from about 300 to about
10,000, or from about 300 to about 5,000, or from about 500 to about
3000.

[0018] The functionalized polymer and/or functionalized copolymer may
comprise one or more carbon-carbon double bonds, and may be reacted with
an enophilic reagent to form a polyfunctionalized polymer and/or
polyfunctionalized copolymer. The enophilic reagent may be reactive
towards one or more of the carbon-carbon double bonds in the
functionalized polymer and/or functionalized copolymer. This provides the
advantage of additional levels of functionality for the functionalized
polymers and/or copolymers. The enophilic reagent may comprise an
oxidizing agent, a sulfurizing agent, a sulfonating agent, an enophilic
acid reagent, an aromatic compound, a hydroxylating agent, a halogenating
agent, or a mixture of two or more thereof. The resulting
polyfunctionalized polymer and/or copolymer may be reacted with one or
more additional reagents (e.g., olefin, acrylic acid, acrylic acid ester,
methacrylic acid, methacrylic acid ester, unsaturated nitrile, vinyl
ester, vinyl ether, halogenated monomer, unsaturated polycarboxylic acid
or derivative thereof, polyhydric alcohol, polyamine, polyalkylene
polyamine, monoisocyanate, diisocyanate, alkenyl-substituted aromatic
compound (e.g., styrene), alkenyl-substituted heterocyclic compound,
organosilane, or a mixture of two or more thereof) to yield additional
polyfunctionalized polymer types.

[0020] The polyfunctionalized monomer may be polymerized to form a
polyfunctionalized polymer. The polyfunctionalized monomer may be
copolymerized with a comonomer to form a polyfunctionalized copolymer.
The comonomer may comprise an olefin, acrylic acid, acrylic acid ester,
methacrylic acid, methacrylic acid ester, unsaturated nitrile, vinyl
ester, vinyl ether, halogenated monomer, unsaturated polycarboxylic acid
or derivative thereof, polyhydric alcohol, polyamine, polyalkylene
polyamine, monoisocyanate, diisocyonate, alkenyl-substituted aromatic
compound (e.g., styrene), alkenyl-substituted heterocyclic compound,
organosilane, or a mixture of two or more thereof. The polyfunctionalized
copolymer may comprise from about 5 to about 99 mole percent, or from
about 5 to about 70 mole percent, or from about 5 to about 50 mole
percent, or from about 5 to about 30 mole percent repeating units derived
from the polyfunctionalized monomer.

[0021] The polyfunctionalized polymer and/or polyfunctionalized copolymer
may have a number average molecular weight in the range from about 300 to
about 50,000, or from about 300 to about 20,000, or from about 300 to
about 10,000, or from about 300 to about 5,000, or from about 500 to
about 3000. These polymers may be reacted with one or more additional
reagents (e.g., olefin, acrylic acid, acrylic acid ester, methacrylic
acid, methacrylic acid ester, unsaturated nitrile, vinyl ester, vinyl
ether, halogenated monomer, unsaturated polycarboxylic acid or derivative
thereof, polyhydric alcohol, polyamine, polyalkylene polyamine,
monoisocyanate, diisocyanate, alkenyl-substituted aromatic compound
(e.g., styrene), alkenyl-substituted heterocyclic compound, organosilane,
or a mixture of two or more there

[0022] This invention relates to a dispersant comprising the reaction
product of a nitrogen-containing reagent or an oxygen-containing reagent,
with: (i) a functionalized monomer comprising a hydrocarbyl group with
one or more carbon-carbon double bonds and one or more functional groups
attached to the hydrocarbyl group, the hydrocarbyl group containing from
about 5 to about 30 carbon atoms, or from about 6 to about 30 carbon
atoms, or from about 8 to about 30 carbon atoms, or from about 10 to
about 30 carbon atoms, or from about 12 to about 30 carbon atoms, or from
about 14 to about 30 carbon atoms, or from about 16 to about 30 carbon
atoms, or from about 5 to about 18 carbon atoms, or from about 12 to
about 18 carbon atoms, or about 18 carbon atoms, the functional group
comprising a carboxylic acid or anhydride; (ii) a polymer derived from
one or more of the functionalized monomers (i); (iii) a copolymer derived
from one or more of the functionalized monomers (i) and one or more
olefin comonomers; (iv) the reaction product of an enophilic acid reagent
with the monomer (i), polymer (ii) and/or copolymer (iii); or (v) a
mixture of two or more of (i), (ii), (iii) and (iv). The olefin comonomer
may contain from 2 to about 30 carbon atoms, or from about 6 to about 24
carbon atoms. The enophilic acid reagent may comprise one or more
alpha-beta unsaturated carboxylic acids and/or derivatives thereof. The
dispersant may be mixed with a succinimide dispersant (e.g.,
polyisobutenyl succinimide).

[0023] This invention relates to a fuel composition, comprising a normally
liquid fuel and one or more of the above-identified dispersants.

[0024] This invention relates to a detergent comprising a neutral or
overbased material derived from a metal or metal compound, and (i) a
functionalized monomer comprising a hydrocarbyl group with one or more
carbon-carbon double bonds and one or more functional groups attached to
the hydrocarbyl group, the hydrocarbyl group containing from about 5 to
about 30 carbon atoms, or from about 6 to about 30 carbon atoms, or from
about 8 to about 30 carbon atoms, or from about 10 to about 30 carbon
atoms, or from about 12 to about 30 carbon atoms, or from about 14 to
about 30 carbon atoms, or from about 16 to about 30 carbon atoms, or from
about 5 to about 18 carbon atoms, or from about 12 to about 18 carbon
atoms, or about 18 carbon atoms, the functional group comprising a
carboxylic acid group or an anhydride thereof; (ii) a polymer derived
from one or more of the functionalized monomers (i); (iii) a copolymer
derived from one or more of the functionalized monomers (i) and one or
more olefin comonomers; (iv) the reaction product of an enophilic acid
reagent with the monomer (i), polymer (ii) and/or copolymer (iii); or (v)
a mixture of two or more of (i), (ii), (iii) and (iv). The olefin
comonomer may contain from 2 to about 30 carbon atoms, or from about 6 to
about 24 carbon atoms. The enophilic acid reagent may comprise one or
more alpha-beta unsaturated carboxylic acids and/or derivatives thereof.
The monomer (i), polymer (ii), copolymer (iii) and/or reaction product
(iv), may be mixed with an alkaryl sulfonic acid (e.g., alkylbenzene
sulfonic acid) prior to or during the formation of the overbased
material.

[0025] This invention relates to a lubricant or functional fluid
composition comprising a base oil. The base oil may comprise a polymer
derived from one or more functionalized monomers, the functionalized
monomer comprising a hydrocarbyl group with one or more carbon-carbon
double bonds and one or more functional groups attached to the
hydrocarbyl group, the hydrocarbyl group containing from about 5 to about
30 carbon atoms, or from about 6 to about 30 carbon atoms, or from about
8 to about 30 carbon atoms, or from about 10 to about 30 carbon atoms, or
from about 12 to about 30 carbon atoms, or from about 14 to about 30
carbon atoms, or from about 16 to about 30 carbon atoms, or from about 5
to about 18 carbon atoms, or from about 12 to about 18 carbon atoms, or
about 18 carbon atoms, the functional group comprising a carboxylic acid
group or a derivative thereof, a hydroxyl group, an amino group, a
carbonyl group, a cyano group, or a mixture of two or more thereof. This
base oil may be blended with an API Group II, Group III, Group IV, or
Group V base oil, or a biologically derived oil. The lubricant or
functional fluid may further comprise one or more of the above-identified
dispersants and/or detergents. These lubricants or functional fluids may
be useful as fill-for-life fluids. The term "fill-for-life-fluid" refers
to lubricants or functional fluids used in sealed systems, such as
bearings, or gear systems that do not require service.

[0026] This invention relates to a lubricant or functional fluid
composition comprising a base oil. The base oil may comprise a copolymer
derived from a functionalized monomer and an olefin comonomer, the
functionalized monomer comprising a hydrocarbyl group with one or more
carbon-carbon double bonds and one or more functional groups attached to
the hydrocarbyl group, the hydrocarbyl group containing from about 5 to
about 30 carbon atoms, or from about 6 to about 30 carbon atoms, or from
about 8 to about 30 carbon atoms, or from about 10 to about 30 carbon
atoms, or from about 12 to about 30 carbon atoms, or from about 14 to
about 30 carbon atoms, or from about 16 to about 30 carbon atoms, or from
about 5 to about 18 carbon atoms, or from about 12 to about 18 carbon
atoms, or about 18 carbon atoms, the functional group comprising a
carboxylic acid group or a derivative thereof, a hydroxyl group, an amino
group, a carbonyl group, a cyano group, or a mixture of two or more
thereof. The copolymer may contain from about 5 to about 70 mole percent,
or from about 5 to about 50 mole percent, or from about 5 to about 30
mole percent, repeating units derived from the functionalized monomer.
The base oil may be blended with an API Group I, Group II, Group III,
and/or Group IV base oil. The lubricant or functional fluid may further
comprise one or more of the above-identified dispersants and/or
detergents. The base oil may be thickened to form a grease composition.

[0027] This invention relates to a polymeric resin comprising a polymer
containing repeating units derived from one or more functionalized
monomers. The functionalized monomer may comprise a hydrocarbyl group
with one or more carbon-carbon double bonds and one or more functional
groups attached to the hydrocarbyl group, the hydrocarbyl group
containing from about 5 to about 30 carbon atoms, or from about 6 to
about 30 carbon atoms, or from about 8 to about 30 carbon atoms, or from
about 10 to about 30 carbon atoms, or from about 12 to about 30 carbon
atoms, or from about 14 to about 30 carbon atoms, or from about 16 to
about 30 carbon atoms, or from about 5 to about 18 carbon atoms, or from
about 12 to about 18 carbon atoms, or about 18 carbon atoms, the
functional group comprising a carboxylic acid group or a derivative
thereof, a hydroxyl group, an amino group, a carbonyl group, a cyano
group, or a mixture of two or more thereof. The functionalized monomer
may comprise a polyfunctionalized monomer wherein the functionalized
monomer is reacted with an enophilic reagent to provide additional
functionality and thereby form a polyfunctionalized monomer. The
enophilic reagent may be reactive towards one or more carbon-carbon
double bonds in the functionalized monomer. The enophilic reagent may
comprise an enophilic acid reagent, an oxidizing agent, an aromatic
compound, a sulfurizing agent, a sulfonating agent, a hydroxylating
agent, a halogenating agent, or a mixture of two or more thereof. The
polymer may comprise a copolymer comprising repeating units derived from
the functionalized monomer and/or the polyfunctionalized monomer, and a
comonomer. The copolymer may comprise from about 5 to about 99 mole
percent, or from about 5 to about 70 mole percent, or from about 5 to
about 50 mole percent, or from about 5 to about 30 mole percent,
repeating units derived from the functionalized monomer and/or
polyfunctionalized monomer. The comonomer may comprise an olefin, acrylic
acid, acrylic acid ester, methacrylic acid, methacrylic acid ester,
unsaturated nitrile, vinyl ester, vinyl ether, halogenated monomer,
unsaturated polycarboxylic acid or derivative thereof, polyhydric
alcohol, polyamine, polyalkylene polyamine, isocyanate, diisocyanate,
alkenyl-substituted aromatic compound (e.g., styrene),
alkenyl-substituted heterocyclic compound, organosilane, or a mixture of
two or more thereof. Polymerization may be effected via the one or more
carbon-carbon double bonds, functional groups and/or additional
functionalities provided by reaction with the enophilic reagent.
Polymerization may be effected through a condensation reaction between
one or more of the functionalized monomers and one or more comonomers.
The polymers or copolymers may be reacted with one or more enophilic
reagents to form one or more polyfunctionalized polymers. The polymer or
copolymer, which may be referred to as a polymeric resin, may be suitable
for use in polymeric or plastic formulations. The polymeric resin may be
useful in forming extruded or molded articles, or for use in
pharmaceuticals, cosmetics, personal care products, adhesives, coating
compositions, including protective and/or decorative coatings (e.g.,
paint), and the like.

[0030] FIG. 3 is a flow sheet showing a metathesis process for
metathesizing natural oil, and then treating the resulting metathesized
natural oil.

DETAILED DESCRIPTION

[0031] All ranges and ratio limits disclosed in the specification and
claims may be combined in any manner. It is to be understood that unless
specifically stated otherwise, references to "a," "an," and/or "the" may
include one or more than one, and that reference to an item in the
singular may also include the item in the plural.

[0032] The term "functional group" is used herein to refer to a group of
atoms in a molecule that is responsible for a characteristic chemical
reaction of that molecule. The functional group may comprise a carboxylic
acid group or derivative thereof, a hydroxyl group, an amino group, a
carbonyl group, a cyano group, or a mixture of two or more thereof. The
functional group may also comprise a carbon-carbon double bond.

[0033] The term "functionalized monomer" refers to a monomer comprising a
hydrocarbyl group and one or more functional groups attached to the
hydrocarbyl group, the hydrocarbyl group containing one or more (e.g., 1
to about 4, or 1 to about 3, or 1 to about 2, or 1) carbon-carbon double
bonds and from about 5 to about 30 carbon atoms, or from about 6 to about
30 carbon atoms, or from about 8 to about 30 carbon atoms, or from about
10 to about 30 carbon atoms, or from about 12 to about 30 carbon atoms,
or from about 14 to about 30 carbon atoms, or from about 16 to about 30
carbon atoms, or from about 5 to about 18 carbon atoms, or from about 12
to about 18 carbon atoms, or about 18 carbon atoms, the functional group
comprising a carboxylic acid group or derivative thereof, a hydroxyl
group, an amino group, a carbonyl group, a cyano group, or a mixture of
two or more thereof. The functionalized monomer may contain from 1 to
about 4 functional groups, or from 1 to about 3, or 1 to about 2, or 1
functional group. Examples of such functionalized monomers may include
alkene substituted carboxylic acids, alkene substituted carboxylic esters
(e.g., unsaturated fatty acids and fatty esters), alkene-substituted
carboxylic acid anhydrides, alkene substituted alcohols, alkene
substituted amines, alkene substituted aldehydes, alkene substituted
amides, alkene substituted imides, mixtures of two or more thereof, and
the like. The functionalized monomer may comprise an ester derived from
the transesterification of an alkene substituted carboxylic ester with an
alcohol. The functionalized monomer may be referred to as being
difunctional or polyfunctional since it has at least one carbon-carbon
double bond and at least one functional group.

[0034] The term "hydrocarbyl" or "hydrocarbyl group" when referring to
groups attached to the remainder of a molecule, refers to one or more
groups having a purely hydrocarbon or predominantly hydrocarbon
character. These groups may include: (1) purely hydrocarbon groups (i.e.,
aliphatic, alicyclic, aromatic, aliphatic- and alicyclic-substituted
aromatic, aromatic-substituted aliphatic and alicyclic groups, as well as
cyclic groups wherein the ring is completed through another portion of
the molecule (that is, any two indicated substituents may together form
an alicyclic group)); (2) substituted hydrocarbon groups (i.e., groups
containing non-hydrocarbon substituents such as hydroxy, amino, nitro,
cyano, alkoxy, acyl, halo, etc.); and (3) hetero groups (i.e., groups
which contain atoms, such as N, O or S, in a chain or ring otherwise
composed of carbon atoms). In general, no more than about three
substituents or hetero atoms, or no more than one, may be present for
each 10 carbon atoms in the hydrocarbyl group. The hydrocarbyl group may
contain one, two, three or four carbon-carbon double bonds.

[0035] The term "carboxylic acid group or derivative thereof" refers to a
carboxylic acid group (e.g., --COOH), or a group that may be derived from
a carboxylic acid group, including a carboxylic acid anhydride group, a
carboxylic ester group (e.g., --COOR), amide group (e.g., --CONR2),
imide group (e.g., --CONRCO--), carbonyl or keto group (e.g., --COR),
aldehyde or formyl group (e.g., --CHO), or a mixture of two or more
thereof. The methods used to form these derivatives may include one or
more of addition, neutralization, overbasing, saponification,
transesterification, esterification, amidification, hydrogenation,
isomerization, oxidation, alkylation, acylation, sulfurization,
sulfonation, rearrangement, reduction, or a combination of two or more
thereof. In the foregoing formulas, R may be hydrogen or a hydrocarbyl
group. When the carboxylic acid derivative group is bivalent, such as
with anhydrides or imides, two hydrocarbyl groups may be attached, at
least one of hydrocarbyl groups containing from about 5 to about 30
carbon atoms, or from about 6 to about 30 carbon atoms, or from about 8
to about 30 carbon atoms, or from about 10 to about 30 carbon atoms, or
from about 12 to about 30 carbon atoms, or from about 14 to about 30
carbon atoms, or from about 16 to about 30 carbon atoms, or from about 5
to about 18 carbon atoms, or from about 12 to about 18 carbon atoms, or
about 18 carbon atoms.

[0036] The term "unsaturated carboxylic acid or derivative thereof" refers
to an unsaturated carboxylic acid, or an unsaturated carboxylic acid
anhydride, ester, amide, imide, aldehyde, ketone, or a mixture of two or
more thereof, that may be derived from the unsaturated carboxylic acid.

[0037] The term "unsaturated fatty acid or derivative thereof" refers to
an unsaturated fatty acid, or an unsaturated fatty anhydride, ester,
amide, imide, aldehyde, ketone, or a mixture of two or more thereof, that
may be derived from the unsaturated fatty acid.

[0038] The term "olefin" is used herein to refer to a compound containing
one or more carbon-carbon double bonds. The olefin may be a monoene
(e.g., ethene), diene (e.g., butadiene), triene (e.g., octatriene),
tetraene (e.g., farnesene), or a mixture of two or more thereof. The
olefin may be a conjugated diene (e.g., 1,3-butadiene).

[0039] The term "olefin comonomer" refers to an olefin of from 2 to about
30 carbon atoms, or from 2 to about 24 carbon atoms, or from about 4 to
about 24 carbon atoms, or from about 6 to about 24 carbon atoms. The
olefin may comprise an alpha olefin, an internal olefin, or a mixture
thereof. The internal olefin may be symmetric or asymmetric. The olefin
may be linear or branched. The olefin may comprise a monoene, diene,
triene, tetraene, or a mixture of two or more thereof. The monoenes may
comprise one or more of ethene, 1-propene, 1-butene, 2-butene, isobutene,
1-pentene, 2-pentene, 3-pentene, cyclopentene, 1-hexene, 2-hexene,
3-hexene, cyclohexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,
2-octene, 3-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene, 1-decene,
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene,
2-methyl-2-butene, 3-methyl-1-butene, 2-methyl-1-pentene,
3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,
3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene,
2,2-dimethyl-3-pentene, styrene, vinyl cyclohexane, or a mixture of two
or more thereof. The dienes, trienes and tetraenes may comprise
butadiene, isoprene, hexadiene, decadiene, octatriene, ocimene,
farnesene, tetraeicosene, or a mixture of two or more thereof. The dienes
may include conjugated dienes, examples of which may include
1,3-butadiene, 1,3-pentadiene, mixtures thereof, and the like.

[0040] The term "normally liquid fuel" is used herein to refer to a fuel
that is liquid at atmospheric pressure and at the temperature at which it
is likely to be stored or used. These may include gasoline and middle
distillate fuels. The normally liquid fuels are distinguished from solid
fuels such as coal and gaseous fuels such as natural gas.

[0042] The term "natural oil derived unsaturated carboxylic acid and/or
derivatives thereof" refers to unsaturated carboxylic acids or
derivatives thereof derived from natural oil. The methods used to form
these natural oil derivatives may include one or more of addition,
neutralization, overbasing, saponification, transesterification,
esterification, amidification, hydrogenation, isomerization, oxidation,
alkylation, acylation, sulfurization, sulfonation, rearrangement,
reduction, or a combination of two or more thereof. Examples of natural
oil derived unsaturated carboxylic acids or derivatives thereof may
include gums, phospholipids, soapstock, acidulated soapstock, distillate
or distillate sludge, unsaturated fatty acids, unsaturated fatty acid
esters, as well as hydroxy substituted variations thereof. The
unsaturated carboxylic acid or derivative thereof, may comprise an alkene
chain in the carboxylic acid or derivative portion of the molecule of
from about 5 to about 30 carbon atoms, or from about 6 to about 30
carbons, or from about 8 to about 30 carbon atoms, or from about 10 to
about 30 carbon atoms, or from about 12 to about 30 carbon atoms, or from
about 14 to about 30 carbons, or from about 16 to about 30 carbon atoms,
or from about 5 to about 18 carbon atoms, or from about 6 to about 24
carbon atoms, or from about 6 to about 18 carbon atoms, or from about 8
to about 24 carbon atoms, or from about 8 to about 18 carbon atoms, or
from about 10 to about 24 carbon atoms, or from about 10 to about 18
carbon atoms, or from about 12 to about 24 carbon atoms, or from about 12
to about 18 carbon atoms, or from about 16 to about 20 carbon atoms, or
from about 12 to about 18 carbon atoms, or from about 15 to about 18
carbon atoms, or about 18 carbon atoms, with one or more carboxylic acid
and/or ester groups, and at least one carbon-carbon double bond in the
alkene chain. The unsaturated carboxylic (e.g., fatty) acid or derivative
thereof may contain an alkene chain with 1 to about 4, or 1 to about 3,
or 1 or 2, or 1 carbon-carbon double bond in the alkene chain. The
natural oil derived unsaturated carboxylic acid or derivative thereof may
comprise an unsaturated fatty acid alkyl (e.g., methyl) ester derived
from a glyceride of natural oil.

[0044] The unsaturated carboxylic (e.g., fatty) acid or derivative thereof
may be functionalized at one or more double bonds in the alkene chain by
reacting it with an enophilic reagent. The enophilic reagent may comprise
an enophilic acid reagent, an oxidizing agent, an aromatic compound, a
sulfurizing agent, a sulfonating agent, a hydroxylating agent, a
halogenating agent, or a mixture of two or more thereof.

[0045] The term "another olefinic compound" is used herein to refer to a
natural oil, a natural oil derived unsaturated carboxylic acid or
derivative thereof, or one of the above-described olefin comonomers.

[0046] The term "metathesis reaction" refers to a catalytic reaction which
involves the interchange of alkylidene units among compounds containing
one or more carbon-carbon double bonds (e.g., olefinic compounds) via the
formation and cleavage of the carbon-carbon double bonds. Metathesis may
occur between two like molecules (often referred to as self-metathesis)
and/or between two different molecules (often referred to as
cross-metathesis).

[0047] The term "metathesis catalyst" refers to any catalyst or catalyst
system that catalyzes a metathesis reaction.

[0048] The terms "metathesize" and "metathesizing" refer to the reacting
of one or more reactant compounds (e.g., a natural oil or natural oil
derived unsaturated carboxylic acid or derivative thereof) in the
presence of a metathesis catalyst to form a metathesized product (e.g.,
metathesized natural oil) comprising one or more metathesis monomers,
oligomers and/or polymers. Metathesizing may refer to self-metathesis or
cross-metathesis. For example, metathesizing may refer to reacting two
triglycerides present in a natural oil (self-metathesis) in the presence
of a metathesis catalyst, wherein each triglyceride has an unsaturated
carbon-carbon double bond, thereby forming a monomer, oligomer and/or
polymer containing bonded groups derived from the triglycerides. The
number of metathesis bonded groups in the metathesized monomers,
oligomers and/or polymers may range from 1 to about 100, or from 2 to
about 50, or from 2 to about 30, or from 2 to about 10. These may include
metathesis monomers, metathesis dimers, metathesis trimers, metathesis
tetramers, metathesis pentamers, as well as high order metathesis
oligomers (e.g., metathesis hexamers, heptamers, octamers, nonamers,
decamers, and the like).

[0049] The term "metathesized natural oil" refers to the product formed
from the metathesis reaction of a natural oil (or a natural oil derived
unsaturated carboxylic acid or derivative thereof) in the presence of a
metathesis catalyst to form one or more functionalized olefins and/or
olefins comprising one or more metathesis monomers, oligomers and/or
polymers derived from the natural oil. The number of metathesis bonded
groups in the metathesized natural oil monomers, oligomers and/or
polymers may range from 1 to about 100, or from 2 to about 50, or from 2
to about 30, or from 2 to about 10. These may include one or more
metathesis monomers, metathesis dimers, metathesis trimers, metathesis
tetramers, metathesis pentamers, and higher order metathesis oligomers or
polymers (e.g., metathesis hexamers, heptamers, octamers, nonamers,
decamers, and the like). The metathesized natural oil may be at least
partially hydrogenated, forming a "hydrogenated metathesized natural
oil." The at least partial hydrogenation step may be conducted prior to
or subsequent to the metathesis reaction. The metathesized natural oil
may be formed from the metathesis reaction of a natural oil comprising
more than one natural oil (e.g., a mixture of soybean oil and palm oil).
The metathesized natural oil may be formed from the metathesis reaction
of a natural oil comprising a mixture of one or more natural oils and one
or more natural oil derivatives. The metathesized natural oil may be in
the form of a liquid or a solid. The solid may comprise a wax.

[0050] The term "metathesized natural oil derived unsaturated carboxylic
acid" refers to an unsaturated carboxylic acid or a derivative thereof
derived from a metathesized natural oil.

[0051] The term "metathesized natural oil derivative" refers to the
product made by the reaction of a metathesized natural oil with a
nitrogen-containing reagent, an oxygen-containing reagent, and/or an
enophilic reagent. The enophilic reagent may comprise an enophilic acid
reagent, oxidizing agent, sulfurizing agent, sulfonating, aromatic
compound, hydroxylating agent, halogenating agent, or a mixture of two or
more thereof. The metathesized natural oil derivative may be in the form
of a liquid or a solid, and may be oil soluble and/or fuel soluble. The
solid may comprise a wax.

[0052] The term "metathesis monomer" refers to a single entity that is the
product of a metathesis reaction which comprises a molecule of a compound
with one or more carbon-carbon double bonds which has undergone an
alkylidene unit interchange via one or more of the carbon-carbon double
bonds either within the same molecule (intramolecular metathesis) and/or
with a molecule of another compound containing one or more carbon-carbon
double bonds such as an olefin (intermolecular metathesis).

[0053] The term "metathesis dimer" refers to the product of a metathesis
reaction wherein two reactant compounds, which can be the same or
different and each with one or more carbon-carbon double bonds, are
bonded together via one or more of the carbon-carbon double bonds in each
of the reactant compounds as a result of the metathesis reaction.

[0054] The term "metathesis trimer" refers to the product of one or more
metathesis reactions wherein three molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the trimer containing three
bonded groups derived from the reactant compounds.

[0055] The term "metathesis tetramer" refers to the product of one or more
metathesis reactions wherein four molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the tetramer containing four
bonded groups derived from the reactant compounds.

[0056] The term "metathesis pentamer" refers to the product of one or more
metathesis reactions wherein five molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the pentamer containing five
bonded groups derived from the reactant compounds.

[0057] The term "metathesis hexamer" refers to the product of one or more
metathesis reactions wherein six molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the hexamer containing six
bonded groups derived from the reactant compounds.

[0058] The term "metathesis heptamer" refers to the product of one or more
metathesis reactions wherein seven molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the heptamer containing seven
bonded groups derived from the reactant compounds.

[0059] The term "metathesis octamer" refers to the product of one or more
metathesis reactions wherein eight molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the octamer containing eight
bonded groups derived from the reactant compounds.

[0060] The term "metathesis nonamer" refers to the product of one or more
metathesis reactions wherein nine molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the nonamer containing nine
bonded groups derived from the reactant compounds.

[0061] The term "metathesis decamer" refers to the product of one or more
metathesis reactions wherein ten molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the decamer containing ten
bonded groups derived from the reactant compounds.

[0062] The term "metathesis oligomer" refers to the product of one or more
metathesis reactions wherein two or more molecules (e.g., 2 to about 10,
or 2 to about 4) of two or more reactant compounds, which can be the same
or different and each with one or more carbon-carbon double bonds, are
bonded together via one or more of the carbon-carbon double bonds in each
of the reactant compounds as a result of the one or more metathesis
reactions, the oligomer containing a few (e.g., 2 to about 10, or 2 to
about 4) bonded groups derived from the reactant compounds.

[0063] The term "metathesis polymer" refers to the product of one or more
metathesis reactions wherein many molecules of two or more reactant
compounds, which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a result
of the one or more metathesis reactions, the polymer containing more than
one (e.g., 2 to about 100, or 2 to about 50, or 2 to about 10, or 2 to
about 4) bonded groups derived from the reactant compounds.

[0064] The term "oil soluble" is used herein to refer to a material which
is soluble in mineral oil to the extent of at least about 10 grams of the
material per liter of mineral oil at a temperature of 20° C., or
at least about 1% by weight.

[0065] The term "fuel soluble" is used herein to refer to a material which
is soluble in a normally liquid fuel (e.g., gasoline and/or middle
distillate) to the extent of at least about 100 mg of the material per
liter of the normally liquid fuel at a temperature of 20° C.

The Functionalized Monomer

[0066] The functionalized monomer may comprise an unsaturated hydrocarbyl
group with one or more attached functional groups. The hydrocarbyl group
may be an alkene group. The hydrocarbyl group may contain from about 5 to
about 30 carbon atoms, or from about 5 to about 18 carbon atoms, or from
about 6 to about 30 carbons, or from about 8 to about 30 carbon atoms, or
from about 10 to about 30 carbon atoms, or from about 12 to about 30
carbon atoms, or from about 14 to about 30 carbons, or from about 16 to
about 30 carbon atoms, or from about 8 to about 24 carbon atoms, or from
about 10 to about 24 carbon atoms, or from about 12 to about 24 carbon
atoms, or from about 8 to about 20 carbon atoms, or from about 10 to
about 20 carbon atoms, or from about 12 to about 20 carbon atoms, or from
about 12 to about 18 carbon atoms, or from about 14 to about 18 carbon
atoms, or from about 15 to about 18 carbon atoms, or from about 16 to
about 18 carbon atoms, or about 18 carbon atoms. The hydrocarbyl group
may be monounsaturated or polyunsaturated with from 1 to about 4
carbon-carbon double bonds, or from 1 to about 3 carbon-carbon double
bonds, or from 1 to about 2 carbon-carbon double bonds, or 1
carbon-carbon double bond. The hydrocarbyl group may contain a
carbon-carbon double bond in the terminal position of the hydrocarbyl
group (e.g., 1-pentenyl, 1-heptenyl, 1-decenyl, 1-dodecenyl,
1-octadecenyl, and the like), and/or one or more internal carbon-carbon
double bonds. The hydrocarbyl group may be linear or branched and may
optionally include one or more functional groups in addition to the
carboxylic acid group or derivative thereof. For example, the hydrocarbyl
group may include one or more hydroxyl groups.

[0067] The functional group may comprise a carboxylic acid group or
derivative thereof, a hydroxyl group, an amino group, a carbonyl group, a
cyano group, or a mixture of two or more thereof. The functional group
may be attached to a terminal carbon atom on the hydrocarbyl group and/or
on an internal carbon atom. The functionalized monomer may contain from 1
to about 4 functional groups, or from 1 to about 3 functional groups, or
1 to about 2 functional groups, or 1 functional group.

[0068] The functionalized monomer may have one or more additional
functional groups attached to the hydrocarbyl group. These may be
provided by reacting the functionalized monomer with an enophilic reagent
which is reactive towards one or more of the carbon-carbon double bonds
in the hydrocarbyl group. The enophilic reagent may be an enophilic acid
reagent, an oxidizing agent, an aromatic compound, a sulfurizing agent, a
sulfonating agent, a hydroxylating agent, a halogenating agent, or a
mixture of two or more thereof.

[0069] The functionalized monomer may be derived from conventional sources
such as natural oil or from a metathesized natural oil. An advantage of
employing a metathesized natural oil is that the structure of the
functionalized monomer may be tailored as a result of the metathesis
process. For example, it may be advantageous to employ a functionalized
monomer with a carbon-carbon double bond in the terminal position of the
structural backbone of the compound. This may be possible to achieve with
the metathesis process. Also, with metathesis, olefins may be separated
from the carboxylic acids or derivatives thereof.

[0071] The natural oil may comprise soybean oil. Soybean oil may comprise
unsaturated glycerides, for example, in many embodiments about 95% weight
or greater (e.g., 99% weight or greater) triglycerides. Major fatty acids
making up soybean oil may include saturated fatty acids, palmitic acid
(hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated
fatty acids, oleic acid (9-octadecenoic acid), linoleic acid
(9,12-octadecadienoic acid), and linolenic acid (9,12,15-octadecatrienoic
acid). Soybean oil may be a highly unsaturated vegetable oil with many of
the triglyceride molecules having at least two unsaturated fatty acids.

[0072] The functionalized monomer may comprise an unsaturated carboxylic
acid or derivative thereof (e.g., anhydride, ester, amide or imide), or
an unsaturated alcohol, amine, aldehyde, ketone, nitrile, or a mixture of
two or more thereof. The unsaturated monomer may comprise a hydrocarbyl
group (e.g., an alkene chain) of from about 5 to about 30 carbon atoms,
or from about 5 to about 18 carbon atoms, or from about 6 to about 30
carbons, or from about 8 to about 30 carbon atoms, or from about 10 to
about 30 carbon atoms, or from about 12 to about 30 carbon atoms, or from
about 14 to about 30 carbons, or from about 16 to about 30 carbon atoms,
or from about 8 to about 24 carbon atoms, or from about 10 to about 24
carbon atoms, or from about 12 to about 24 carbon atoms, or from about 8
to about 20 carbon atoms, or from about 10 to about 20 carbon atoms, or
from about 12 to about 20 carbon atoms, or from about 12 to about 18
carbon atoms, or from about 14 to about 18 carbon atoms, or from about 15
to about 18 carbon atoms, or from about 16 to about 18 carbon atoms, or
about 18 carbon atoms, with one or more functional groups, and at least
one carbon-carbon double bond in the hydrocarbyl group or alkene chain.
The unsaturated carboxylic acid or derivative thereof may be a
monounsaturated or polyunsaturated carboxylic acid or derivative thereof
with, for example, an alkene chain containing from 1 to about 4
carbon-carbon double bonds.

[0073] The functionalized monomer may comprise an olefin chain with 1, 2,
3 or 4 carbon-carbon double bonds in the chain. The olefin chain may be
derived from pentene, hexene, heptene, octene, nonene, decene, undecene,
dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene,
octadecene, or a mixture of two or more thereof. The olefin chain may
comprise octadiene, nonadiene, decadiene, undecadiene, dodecadiene,
tridecadiene, tetradecadiene, pentadecadiene, tetradecatriene,
pentadecatriene, hexadecatriene, heptadecatriene, octadecatriene,
tetradecatetraene, pentadecatetraene, hexadecatetraene,
heptadecatetraene, octadecatetraene, or a mixture of two or more thereof.
The olefin chain may be derived from nonene, decene, dodecene,
octadecene, or a mixture of two or more thereof.

[0074] The functionalized monomer may comprise a polyunsaturated fatty
acid or polyunsaturated fatty ester. The polyunsaturated fatty ester may
be a "polyunsaturated monoester" and/or "polyunsaturated polyol esters."
Polyunsaturated monoesters may comprise polyunsaturated fatty acids that
are esterified with monofunctional alcohols. These alcohols may contain
from 1 to about 20 carbon atoms, or from 1 to about 12 carbon atoms, or
from 1 to about 8 carbon atoms, or from 1 to about 4 carbon atoms, and
may include methanol, ethanol, propanol, butanol, mixtures of two or more
thereof, and the like. Polyunsaturated polyol esters may have at least
one polyunsaturated fatty acid that is esterified by the hydroxyl group
of polyol. The polyol may contain from 2 to about 10 carbon atoms, and
from 2 to about 6 hydroxyl groups. Examples may include ethylene glycol,
glycerol, trimethylolpropane, 1,2-propanediol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,
2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,
2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures of
two or more thereof, and the like.

[0075] The polyunsaturated fatty acid and/or ester may have a straight
alkene chain and may be represented by the formula:

CH3--(CH2)n1--[--(CH2)n3--CH═CH--]x--(-
CH2)n2--COOR

[0076] where: [0077] R is hydrogen (fatty acid), or an aliphatic or
aromatic group (fatty ester); [0078] n1 is an integer equal to or greater
than 0 (typically 0 to 15; more typically 0, 3, or 6); [0079] n2 is an
integer equal to or greater than 0 (typically 2 to 11; more typically 3,
4, 7, 9, or 11); [0080] n3 is an integer equal to or greater than 0
(typically 0 to 6; more typically 1); and [0081] x is an integer equal to
or greater than 2 (typically 2 to 6, more typically 2 to 3).

[0082] The polyunsaturated fatty acids and esters may include those
provided in the following Table A.

[0083] Polyunsaturated monoesters may be alkyl esters (e.g., methyl
esters) or aryl esters and may be derived from polyunsaturated fatty
acids or polyunsaturated glycerides by transesterifying with a monohydric
alcohol. The monohydric alcohol may be any monohydric alcohol that is
capable of reacting with the unsaturated free fatty acid or unsaturated
glyceride to form the corresponding unsaturated monoester. The monohydric
alcohol may be a C1 to C20 monohydric alcohol, or a C1 to
C12 monohydric alcohol, or a C1 to C8 monohydric alcohol,
or a C1 to C4 monohydric alcohol. The carbon atoms of the
monohydric alcohol may be arranged in a straight chain or in a branched
chain structure, and may be substituted with one or more substituents.
Representative examples of monohydric alcohols include methanol, ethanol,
propanol (e.g., isopropanol), butanol, mixtures of two or more thereof,
and the like.

[0084] The functionalized monomer may comprise a transesterified
polyunsaturated triglyceride. Transesterification of a polyunsaturated
triglyceride may be represented as follows.

Depending upon the make-up of the polyunsaturated triglyceride, the above
reaction may yield one, two, or three moles of polyunsaturated monoester.
Transesterification may be conducted in the presence of a catalyst, for
example, alkali catalysts, acid catalysts, or enzymes. Representative
alkali transesterification catalysts may include NaOH, KOH, sodium and
potassium alkoxides (e.g., sodium methoxide), sodium ethoxide, sodium
propoxide, sodium butoxide. Representative acid catalysts may include
sulfuric acid, phosphoric acid, hydrochloric acid, and sulfonic acids.
Organic or inorganic heterogeneous catalysts may also be used for
transesterification. Organic heterogeneous catalysts may include sulfonic
and fluorosulfonic acid-containing resins. Inorganic heterogeneous
catalysts may include alkaline earth metals or their salts such as CaO,
MgO, calcium acetate, barium acetate, natural clays, zeolites, Sn, Ge or
Pb, which may be supported on various support materials such as ZnO, MgO,
TiO2, activated carbon or graphite, inorganic oxides such as
alumina, silica-alumina, boria, and the like. The catalysts may comprise
one or more of P, Ti, Zr, Cr, Zn, Mg, Ca, Fe, or an oxide thereof. The
triglyceride may be transesterified with methanol (CH3OH) in order
to form free fatty acid methyl esters.

[0085] The polyunsaturated fatty esters may comprise polyunsaturated
polyol esters. The polyunsaturated polyol ester compounds may have at
least one polyunsaturated fatty acid that is esterified by the hydroxyl
group of a polyol. The other hydroxyl groups of the polyol may be
unreacted, may be esterified with a saturated fatty acid, or may be
esterified with a monounsaturated fatty acid. Examples of polyols include
glycerol and 1,3 propanediol, as well as those mentioned above. The
unsaturated polyol esters may have the general formula:

R(O--Y)m(OH)n(O--X)b

[0086] where [0087] R is an organic group having a valency of (n+m+b);
[0088] m is an integer from 0 to (n+m+b-1), typically 0 to 2; [0089] b is
an integer from 1 to (n+m+b), typically 1 to 3; [0090] n is an integer
from 0 to (n+m+b-1), typically 0 to 2; [0091] (n+m+b) is an integer that
is 2 or greater; [0092] X is
--(O)C--(CH2)n2--[--CH═CH--(CH2)n3--]x--(CH.-
sub.2)n1--CH3; [0093] Y is --(O)C--R'; [0094] R' is a straight
or branched chain alkyl or alkenyl group; [0095] n1 is an integer equal
to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6);
[0096] n2 is an integer equal to or greater than 0 (typically 2 to 11;
more typically 3, 4, 7, 9, or 11); [0097] n3 is an integer equal to or
greater than 0 (typically 0 to 6; more typically 1); and [0098] x is an
integer equal to or greater than 2 (typically 2 to 6, more typically 2 to
3).

[0099] The polyunsaturated polyol esters may be polyunsaturated
glycerides. The term "polyunsaturated glyceride" refers to a polyol ester
having at least one (e.g., 1 to 3) polyunsaturated fatty acid that is
esterified with a molecule of glycerol. The fatty acid groups may be
linear or branched and may include pendant hydroxyl groups. The
polyunsaturated glycerides may be represented by the general formula:

CH2A-CHB--CH2C [0100] where -A; --B; and --C are selected
from [0101] --OH; [0102]
--O(O)C--(CH2)n2--[--CH═CH--(CH2)n3--]x--(CH-
2)n1--CH3; and [0103] --O(O)C--R'; [0104] with the
proviso that at least one of -A, --B, or --C is [0105]
--O(O)C--(CH2)n2--[--CH═CH--(CH2)n3--]x--(CH-
2)n1--CH3. [0106] In the above formula: [0107] R' is a
straight or branched chain alkyl or alkenyl group; [0108] n1 is an
integer equal to or greater than 0 (typically 0 to 15; more typically 0,
3, or 6); [0109] n2 is an integer equal to or greater than 0 (typically 2
to 11; more typically 3, 4, 7, 9, or 11); [0110] n3 is an integer equal
to or greater than 0 (typically 0 to 6; more typically 1); and [0111] x
is an integer equal to or greater than 2 (typically 2 to 6, more
typically 2 to 3).

[0112] Polyunsaturated glycerides having two --OH groups (e.g., -A and --B
are --OH) may be referred to as unsaturated monoglycerides. Unsaturated
glycerides having one --OH group may be referred to as unsaturated
diglycerides. Unsaturated glycerides having no --OH groups may be
referred to as unsaturated triglycerides.

[0113] The polyunsaturated glyceride may include monounsaturated fatty
acids, polyunsaturated fatty acids, and saturated fatty acids that are
esterified with the glycerol molecule. The main chain of the individual
fatty acids may have the same or different chain lengths. Accordingly,
the unsaturated glyceride may contain up to three different fatty acids
so long as at least one fatty acid is a polyunsaturated fatty acid.

[0114] The functionalized monomer may comprise a Δ9 polyunsaturated
fatty acid, a Δ9 polyunsaturated fatty ester (e.g., monoesters or
polyol esters), or a mixture thereof. Δ9 polyunsaturated fatty
acids and/or esters may have at least two carbon-carbon double bonds with
one carbon-carbon double bond being located between the 9th and
10th carbon atoms (i.e., between C9 and C10) in the alkene
chain of the polyunsaturated fatty acid and/or ester. In determining this
position, the alkene chain is numbered starting with the carbon atom of
the carbonyl group of the unsaturated fatty acid and/or ester. Included
within the definition of Δ9 polyunsaturated fatty acids and/or
esters are Δ9, Δ12 polyunsaturated fatty acids and/or esters,
and Δ9, Δ12, Δ15 polyunsaturated fatty acids and/or
esters and carboxylate salts.

[0115] The Δ9 polyunsaturated acid or ester may have a straight
alkene chain and may be represented by the structure:

CH3--(CH2)n1--[--(CH2)n3--CH═CH--]x--(-
CH2)7--COOR

[0116] where [0117] R is hydrogen (fatty acid), or an aliphatic group
(fatty monoester); [0118] n1 is an integer equal to or greater than 0
(typically 0 to 6; or 0, 3 or 6); [0119] n3 is an integer equal to or
greater than 0 (typically 1); and [0120] x is an integer equal to or
greater than 2 (typically 2 to 6, more typically 2 to 3).

[0121] The Δ9 polyunsaturated fatty acid and/or ester may have a
total of about 12, 15 or 18 carbons in the alkene chain. Examples may
include

CH3--(CH2)4--CH═CH--CH2--CH═CH--(CH2).s-
ub.7--COOR;

CH3--CH2--CH═CH--CH2--CH═CH--CH2--CH═CH--
-(CH2)7--COOR.

CH2═CH--CH2--CH═CH--(CH2)7--COOR; and

CH2═CH--CH2--CH═CH--CH2--CH═CH--(CH2).su-
b.7--COOR, [0122] where R is hydrogen (fatty acid), or an aliphatic
group (fatty monoester); Δ9 unsaturated fatty esters may be
monoesters or polyol esters. The Δ9 unsaturated polyol ester may
have the general structure

[0122] CH2A-CHB--CH2C [0123] where -A; --B; and --C are
independently selected from [0124] --OH; [0125] --O(O)C--R'; and [0126]
--O(O)C--(CH2)7--[--CH═CH--CH2--]x---(CH2).s-
ub.n1CH3[0127] with the proviso that at least one of -A, --B, or
--C is [0128]
--O(O)C--(CH2)7--[--CH═CH--CH2--]x---(CH2).s-
ub.n1CH3[0129] In the above formula: [0130] R' is a straight or
branched chain alkyl or alkenyl group; [0131] n1 is independently an
integer equal to or greater than 0 (typically 0 to 6); and [0132] x is an
integer greater than or equal to 2 (typically 2 to 6, more typically 2 to
3).

[0136] The functionalized monomer may comprise an unsaturated carboxylic
acid and/or ester used with an alkene chain of from about 10 to about 30
carbon atoms, or from about 10 to about 24 carbon atoms, or about 18
carbon atoms, and a carbon-carbon double bond between the C9 and
C10 carbon atoms in the alkene chain.

[0137] The functionalized monomer may comprise an unsaturated fatty acid
and/or the unsaturated fatty ester with an alkene chain of from 8 to
about 30 carbon atoms, or from about 8 to about 18 carbon atoms, or about
18 carbon atoms, and a carbon-carbon double bond between the C6 and
C7 carbon atoms in the alkene chain.

[0138] The functionalized monomer may comprise an unsaturated fatty acid
and/or unsaturated fatty ester with an alkene chain of about 14 to about
30 carbon atoms, or from about 14 to about 18 carbon atoms, or about 18
carbon atoms, and a carbon-carbon double bond between the C12 and
C13 carbon atoms in the alkene chain.

[0139] The functionalized monomer may comprise an unsaturated fatty acid
and/or unsaturated fatty ester with an alkene chain of from about 16 to
about 30 carbon atoms, or from about 16 to about 18 carbon atoms, or
about 18 carbon atoms, and a carbon-carbon double bond between the
C15 and C16 carbon atoms in the alkene chain.

[0140] The functionalized monomer may comprise an unsaturated fatty acid
and/or unsaturated fatty ester with an alkene chain of from 14 to about
30 carbon atoms, or from about 14 to about 18 carbon atoms, or about 18
carbon atoms, and carbon-carbon double bonds between the C9 and
C10 carbon atoms and between the C12 and C13 carbon atoms
in the alkene chain.

[0141] The functionalized monomer may comprise an unsaturated fatty acid
and/or the unsaturated fatty ester with an alkene chain of from 16 to
about 30 carbon atoms, or from about 16 to about 18 carbon atoms, or
about 18 carbon atoms, with carbon-carbon double bonds between the
C9 and C10 carbon atoms, between the C12 and C13
carbon atoms, and between C15 and C16 carbon atoms in the
alkene chain.

[0142] The functionalized monomer may comprise an unsaturated fatty acid
and/or unsaturated fatty ester with an alkene chain from 16 to about 30
carbon atoms, or from about 16 to about 18 carbon atoms, or about 18
carbon atoms, and carbon-carbon double bonds between the C6 and
C7 carbon atoms, between the C9 and C10 carbon atoms,
between the C12 and C13 carbon atoms, and between the C15
and C16 carbon atoms in the alkene chain.

[0147] The functionalized monomer may comprise a metathesized natural oil
derived unsaturated carboxylic acid and/or ester. The metathesized
natural oil derived unsaturated carboxylic acid and/or ester may be
produced using a self-metathesis process, a cross-metathesis process, or
a combination thereof. The self-metathesis process may comprise reacting
a natural oil or natural oil derived unsaturated carboxylic acid and/or
ester in the presence of a metathesis catalyst to form a metathesized
natural oil from which the metathesized natural oil derived unsaturated
carboxylic acid and/or ester may be derived.

[0148] The cross-metathesis process may comprise reacting a natural oil or
natural oil derivative with another olefinic compound in the presence of
a metathesis catalyst to form the metathesized natural oil. The another
olefinic compound may be a natural oil, a natural oil derivative or a
short chain olefin. The short chain olefin may comprise an alpha olefin,
an internal olefin, or a mixture thereof. The internal olefin may be
symmetric or asymmetric. The olefin may comprise one or more of ethene,
propene, 2-butene, 3-hexene, 4-octene, 2-pentene, 2-hexene, 2-heptene,
3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 4-nonene, ethylene,
1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene, or a mixture of
two or more thereof.

[0149] Multiple, sequential metathesis reaction steps may be employed. For
example, the metathesized natural oil or metathesized natural oil derived
unsaturated carboxylic acid and/or ester may be made by reacting a
natural oil or natural oil derived unsaturated carboxylic acid and/or
ester in the presence of a metathesis catalyst to form a first
metathesized natural oil or first metathesized natural oil derived
unsaturated carboxylic acid and/or ester. The first metathesized natural
oil or first metathesized natural oil derived unsaturated carboxylic acid
and/or ester may then be reacted in a self-metathesis reaction to form
another metathesized natural oil or metathesized natural oil derived
unsaturated carboxylic acid and/or ester. Alternatively, the first
metathesized natural oil or metathesized natural oil derived unsaturated
carboxylic acid and/or ester may be reacted in a cross-metathesis
reaction with a natural oil and/or natural oil derived unsaturated
carboxylic acid and/or ester to form another metathesized natural oil or
metathesized natural oil derived unsaturated carboxylic acid and/or
ester. These procedures may be used to form metathesis dimers, trimers as
well as higher order metathesis oligomers and polymers. These procedures
can be repeated as many times as desired (for example, from 2 to about 50
times, or from 2 to about 30 times, or from 2 to about 10 times, or from
2 to about 5 times, or from 2 to about 4 times, or 2 or 3 times) to
provide the desired metathesis oligomer or polymer which may comprise,
for example, from 2 to about 100 bonded groups, or from 2 to about 50, or
from 2 to about 30, or from 2 to about 10, or from 2 to about 8, or from
2 to about 6 bonded groups, or from 2 to about 4 bonded groups, or from 2
to about 3 bonded groups.

[0150] The metathesized natural oil or metathesized natural oil derived
unsaturated carboxylic acid and/or ester produced by the metathesis
reaction process may comprise a mixture of carboxylic acids and/or
esters, and olefins, comprising one or more metathesis monomers,
oligomers and/or polymers derived from the unsaturates in the natural
oil. The number of bonded groups in the metathesized natural oil
monomers, oligomers or polymers may range from 1 to about 100, or from 2
to about 50, or from 2 to about 30, or from 2 to about 10. These may
include metathesis monomers, metathesis dimers, metathesis trimers,
metathesis tetramers, metathesis pentamers, and higher order metathesis
oligomers or polymers (e.g., metathesis hexamers, heptamers, octamers,
nonamers, decamers, and the like). These may be useful as the
functionalized polymers or copolymers of the invention.

[0151] The metathesis starting materials or reactants may be subjected to
a metathesis reaction to produce the desired metathesized product.
Metathesis is a catalytic reaction that involves the interchange of
alkylidene units among compounds containing one or more double bonds
(i.e., olefinic compounds) via the formation and cleavage of the
carbon-carbon double bonds. Metathesis can occur between two of the same
molecules (often referred to as self-metathesis) and/or it can occur
between two different molecules (often referred to as cross-metathesis).

[0152] Self-metathesis may be represented generally as shown in Equation
I.

R1--HC═CH--R2+R1--CH═CH--R2R1--CH═C-
H--R1+R2--CH═CH--R2 (I) [0153] where R1 and
R2 are organic groups. Cross-metathesis may be represented generally
as shown in Equation II.

[0155] When an unsaturated polyol ester comprises molecules having more
than one carbon-carbon double bond, self-metathesis may result in
oligomerization or polymerization of the unsaturates in the starting
material. For example, reaction sequence (III) depicts metathesis
oligomerization of a representative species (e.g., an unsaturated polyol
ester) having more than one carbon-carbon double bond. In reaction
sequence (III), the self-metathesis reaction results in the formation of
metathesis dimers, metathesis trimers, and metathesis tetramers. Although
not shown, higher order oligomers such as metathesis pentamers, hexamers,
heptamers, octamers, nonamers, decamers, and mixtures of two or more
thereof, may also be formed. The number of metathesis repeating units or
groups in the metathesized oil may range from 1 to about 100, or from 2
to about 50, or from 2 to about 30, or from 2 to about 10, or from 2 to
about 4. The molecular weight of the metathesis dimer may be greater than
the molecular weight of the unsaturated polyol ester from which the dimer
is formed. Each of the bonded polyol ester molecules may be referred to
as a "repeating unit or group." Typically, a metathesis trimer may be
formed by the cross-metathesis of a metathesis dimer with an unsaturated
polyol ester. Typically, a metathesis tetramer may be formed by the
cross-metathesis of a metathesis trimer with an unsaturated polyol ester
or formed by the cross-metathesis of two metathesis dimers.

[0157] An unhydrogenated or partially hydrogenated polyol ester may be
subjected to metathesis (self or cross). An exemplary self-metathesis
reaction scheme is shown in FIG. 1. The reaction scheme shown in FIG. 1
highlights the reaction of the major fatty acid group component of the
hydrogenation product composition (i.e., triacylglycerides having a
monounsaturated fatty acid group). As shown in FIG. 1, a triglyceride
having a monounsaturated fatty acid group is self-metathesized in the
presence of a metathesis catalyst to form a metathesis product
composition. Within FIG. 1, the R group designates a diglyceride. In FIG.
1, the reactant composition A comprises triglyceride having a
monounsaturated fatty acid group. The resulting metathesized product
composition includes, as major components, monounsaturated diacid esters
in triglyceride form B, internal olefins C and monounsaturated fatty acid
esters in triglyceride form D. Any one or more of the starting material A
and each of the products shown, B, C and D, may be present as the cis or
trans isomer. Unreacted starting material may also be present (not
shown). As illustrated, the metathesized products, B, C and D may have
overlapping chain lengths.

[0158] A concern when performing metathesis of natural oils in their
triglyceride or other form may be the generation light co-products.
Naturally occurring methylene interrupted cis, cis configuration may form
cyclic compounds that may be present as volatile organic compounds
(VOCs). Depending upon the identity and amount of the VOC, it may
represent a yield loss and/or a hazardous emission. It may thus be
desirable to reduce the formation of VOCs during the metathesis reaction.
As the concentration of polyunsaturates is reduced, this in turn reduces
the likelihood of generating such metathesis products as cyclohexadienes
(e.g., 1,3-cyclohexadiene, 1,4-cyclohexadiene, and the like), which
themselves can be VOCs and/or be converted to other VOCs, such as
benzene. Thus, in some aspects, the metathesis process may reduce the
generation of VOCs and/or control the identity of any yield loss that can
result from the metathesis reaction.

[0159] In some aspects, then, the invention can provide methods wherein
the occurrence of methylene interrupted cis-cis diene structures may be
reduced in the metathesis reaction mixture. These structures may be
converted to other structures by geometric isomerization, positional
isomerization, and/or hydrogenation. In turn, these methods may reduce
volatile co-product formation, e.g., in the form of cyclohexadiene.

[0160] An exemplary cross-metathesis reaction scheme is illustrated in
FIG. 2. As shown in FIG. 2, a triglyceride having a monounsaturated fatty
acid group is cross-metathesized with a short chain olefin (ethylene
shown in figure), in the presence of a metathesis catalyst to form a
metathesis product composition. The short chain olefins may include, for
example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,
2-pentene, isopentene, 2-hexene, 3-hexene, and the like.

[0161] As shown in FIG. 2, the reactant composition E includes
triglyceride having a monounsaturated fatty acid group and ethylene. The
resulting metathesized product composition includes, as major components,
monounsaturated fatty acid esters in triglyceride form having terminal
double bonds F, as well as olefins with terminal double bonds G.
Unreacted starting material can also be present, as well as products from
some amount of self-metathesis (not shown in figure). The starting
material and each of the products shown, E and F, may be present as the
cis or trans isomer (except when ethylene is used in which case the
product is a terminal olefin). As illustrated, the metathesized products,
E and F, may have overlapping chain lengths. The chain lengths of the
terminal monounsaturated fatty acid esters may be in the range from about
5 to about 17 carbons. In some aspects, the majority (e.g., 50% or more)
of the terminal monounsaturated fatty acids may have chain lengths in the
range of from about 9 to about 13 carbon atoms.

[0162] The metathesis process can be conducted under any conditions
adequate to produce the desired metathesis products. For example,
stoichiometry, atmosphere, solvent, temperature and pressure can be
selected to produce a desired product and to minimize undesirable
byproducts. The metathesis process may be conducted under an inert
atmosphere. Similarly, if the olefin reagent is supplied as a gas, an
inert gaseous diluent can be used. The inert atmosphere or inert gaseous
diluent typically is an inert gas, meaning that the gas does not interact
with the metathesis catalyst to substantially impede catalysis. For
example, particular inert gases are selected from the group consisting of
helium, neon, argon, nitrogen and combinations thereof.

[0163] Similarly, if a solvent is used, the solvent chosen may be selected
to be substantially inert with respect to the metathesis catalyst. For
example, substantially inert solvents include, without limitation,
aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.;
halogenated aromatic hydrocarbons, such as chlorobenzene and
dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane,
cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane,
chloroform, dichloroethane, etc.

[0164] In certain embodiments, a ligand may be added to the metathesis
reaction mixture. In many embodiments using a ligand, the ligand is
selected to be a molecule that stabilizes the catalyst, and may thus
provide an increased turnover number for the catalyst. In some cases the
ligand can alter reaction selectivity and product distribution. Examples
of ligands that can be used include Lewis base ligands, such as, without
limitation, trialkylphosphines, for example tricyclohexylphosphine and
tributyl phosphine; triarylphosphines, such as triphenylphosphine;
diarylalkylphosphines, such as, diphenylcyclohexylphosphine; pyridines,
such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as other
Lewis basic ligands, such as phosphine oxides and phosphinites. Additives
may also be present during metathesis that increase catalyst lifetime.

[0165] Any useful amount of the selected metathesis catalyst can be used
in the process. For example, the molar ratio of the unsaturated polyol
ester to catalyst may range from about 5:1 to about 10,000,000:1, or from
about 50:1 to 500,000:1.

[0166] The metathesis reaction temperature may be a rate-controlling
variable where the temperature is selected to provide a desired product
at an acceptable rate. The metathesis temperature may be greater than
-40° C., may be greater than about -20° C., and is
typically greater than about 0° C. or greater than about
20° C. Typically, the metathesis reaction temperature is less than
about 150° C., typically less than about 120° C. An
exemplary temperature range for the metathesis reaction may range from
about 20° C. to about 120° C.

[0167] The metathesis reaction can be run under any desired pressure.
Typically, it will be desirable to maintain a total pressure that is high
enough to keep the cross-metathesis reagent in solution. Therefore, as
the molecular weight of the cross-metathesis reagent increases, the lower
pressure range typically decreases since the boiling point of the
cross-metathesis reagent increases. The total pressure may be selected to
be greater than about 10 kPa, in some embodiments greater than about 30
kPa, or greater than about 100 kPa. Typically, the reaction pressure is
no more than about 7000 kPa, in some embodiments no more than about 3000
kPa. An exemplary pressure range for the metathesis reaction is from
about 100 kPa to about 3000 kPa. In some embodiments, it may be desirable
to conduct self-metathesis under vacuum conditions, for example, at low
as about 0.1 kPa.

[0168] A process for metathesizing a natural and treating the resulting
metathesized natural oil is illustrated in FIG. 3. In this process, the
metathesized natural oil is separated into olefins, and carboxylic acids
and/or esters which may then undergo subsequent treatment. Referring to
FIG. 3, natural oil reactant 12 may be reacted with itself, or optionally
with another olefinic compound 14, in metathesis reactor 20 in the
presence of a metathesis catalyst. The natural oil reactant 12 may
undergo a self-metathesis reaction, or it may undergo a cross-metathesis
reaction with the another olefinic compound 14. The natural oil reactant
12 may undergo both self- and cross-metathesis reactions in separate
metathesis reactors. Multiple parallel or sequential metathesis reactions
may be conducted. The self-metathesis and/or cross-metathesis reactions
may be used to form a metathesized natural oil product 22. The
metathesized natural oil product 22 may comprise one or more olefins 32
and one or more carboxylic acids and/or esters. The metathesized natural
oil product 22 may undergo a separation process in separation unit 30 to
form olefin stream 32, and carboxylic acid and/or ester stream 34.
Separation unit 30 may comprise a distillation unit.

[0169] The olefins from 32 and/or olefins from downstream of 32 (e.g., 42,
etc.) may be used as a source of olefin comonomers in forming the
functionalized copolymer of the present invention. The carboxylic acids
and/or esters from 34 and/or from downstream of 34 (e.g., 72, etc.) may
be used as a source of the functionalized monomers of the present
invention.

[0170] The use of branched short chained olefins in the metathesis
reaction may provide for the formation of a metathesized natural oil
product with branched olefins. These may be subsequently hydrogenated to
form iso-paraffins. The branched short chain olefins may be useful for
providing desired performance properties for middle distillate fuels such
as jet fuels, kerosene, diesel fuel, and the like.

[0171] It may be possible to use a mixture of various linear or branched
short chain olefins in the metathesis reaction to achieve a desired
product distribution. For example, a mixture of butenes (e.g., 1-butene,
2-butene, and, optionally, isobutene) may be employed as the another
olefinic compound. This may allow for the use of a low cost, commercially
available feedstock instead of a purified source of one particular
butene. These low cost butene feedstocks may be diluted with n-butane
and/or isobutane.

[0172] Recycled streams from downstream separation units may be combined
with the reactant 12 and, optionally, the another olefinic compound 14,
in the metathesis reactor 20. For example, a low molecular weight (e.g.,
C2-C6) olefin stream 44 and bottoms (e.g., C15+) olefin
stream 46 from separation unit 40 may be recycled to the metathesis
reactor 20.

[0173] The metathesized natural oil product 22 may flow through a flash
vessel or flash drum (not shown in FIG. 3) operated under temperature and
pressure conditions that may be used to target C2 or C2-C3
olefin compounds as light ends. These compounds may be flashed off and
removed. The light ends may be sent to another separation unit (now shown
in FIG. 3), where the C2 or C2-C3 olefin compounds may be
further separated from higher molecular weight or heavier compounds that
may have flashed off with the C2 or C2-C3 olefin
compounds. The heavier compounds may comprise, for example,
C3-C5 olefin compounds. After separation, the C2 or
C2-C3 olefins may be used as the olefin comonomer of the
present invention. Alternatively, these olefins may be used for other
applications or as a fuel source. The bottoms stream from the flash
vessel or flash drum may contain mostly C3-C5 olefin compounds
which may be used as the olefin comonomer of the present invention,
returned as a recycle stream to the metathesis reactor 20, or separated
from the process and used for other applications or as a fuel source. The
metathesized natural oil product 22 that does not flash in the flash
vessel or flash drum may be advanced downstream to separation unit 30.

[0174] The metathesized natural oil product 22 may be treated in an
adsorbent bed to facilitate the separation of the metathesized natural
oil product 22 from the metathesis catalyst prior to entering the flash
vessel or drum and/or prior to entering separation unit 30. The adsorbent
may comprise a clay bed. The clay bed may adsorb the metathesis catalyst.
After a filtration step, the metathesized natural oil product 22 may be
sent to the flash vessel or flash drum and/or to the separation unit 30.
Alternatively, the adsorbent may comprise a water soluble phosphine
reagent such as trishydroxymethyl phosphine (THMP). The catalyst may be
separated using the water soluble phosphine via liquid-liquid extraction.
Alternatively, the metathesized natural oil product 22 may be reacted
with a reagent to deactivate or to extract the catalyst.

[0175] In the separation unit 30, the metathesized natural oil product 22
may be separated into two or more product streams, these product streams
comprising olefin stream 32, and carboxylic acid and/or ester stream 34.
In an embodiment, a byproduct stream comprising desired olefins, and/or
acids and/or esters may be removed in a side-stream from the separation
unit 30. The separated olefins 32 may comprise hydrocarbons with carbon
numbers up to, for example, about 24, or higher. The carboxylic acids
and/or esters 34 may comprise one or more metathesized glycerides. The
olefins 32 may be separated or distilled overhead for processing into
olefin compositions, while the carboxylic acids and/or esters 34 may be
drawn into a bottoms stream. Based on the quality of the separation, it
is possible for some lighter acids and/or esters to be carried into the
olefin stream 32, and it is also possible for some heavier olefins to be
carried into the acid and/or ester stream 34.

[0176] The olefins 32 may be collected and sold for any number of known
uses and/or used as a source of the olefin comonomers in accordance with
the present invention. The olefins 32 may be further processed in an
olefin separation unit 40 and/or in separation unit 60.

[0177] The carboxylic acids and/or esters 34 may comprise one or more
unsaturated carboxylic acids, and/or one or more unsaturated carboxylic
esters. These may include glycerides and free fatty acids. The acids
and/or esters 34 may be separated or distilled for further processing
into various products and/or used as a source of functionalized monomers
in accordance with the present invention. In an embodiment, further
processing may target, for example, C5-C18 fatty acids and/or
C5-C18 fatty acid esters. These may include fatty acid methyl
esters, such as 9-decenoic acid (9DA) esters, 10-undecenoic acid (10UDA)
esters, 9-dodecenoic acid (9DDA) esters and/or 9-octadecenoic (9ODA)
esters; 9DA, 10UDA, 9DDA and/or 9ODA; and/or diesters of transesterified
products; or mixtures of two or more thereof. Further processing may
target, for example, the production of diacids, anhydrides, diesters,
amides, imides, and the like. These may be used as the functionalized
monomers in accordance with the present invention.

[0178] The olefins 32 may be further separated or distilled in the olefin
separation unit 40. Light end olefins, which may comprise, for example,
C2-C9 olefins, or C3-C8 olefins, may be distilled
into an overhead stream 44. Heavier olefins (e.g., C16+ olefins) in
olefin bottoms stream 46 may be combined with the light end olefin stream
44 to assist in targeting a specific monomer composition. The light end
olefins 44 may be recycled to the metathesis reactor 20 and/or purged
from the system for further processing. The light end olefins 44 may be
partially purged from the system and partially recycled to the metathesis
reactor 20. The olefin bottoms stream 46 may be purged and/or recycled to
the metathesis reactor 20 for further processing. The light end olefins
44 and/or olefin bottoms stream 46 may be used as the olefin comonomers
of the present invention. A center-cut olefin stream 42 may be separated
in the olefin distillation unit 40 and subjected to further processing.
The center-cut olefins 42 may be used to target a selected olefin
distribution for a specific end use. For example, the center cut stream
42 may comprise a C6-C24 olefin distribution which may be used
as the olefin comonomers in accordance with the present invention. A
C5-C15 olefin distribution may be targeted for further
processing as a naphtha-type jet fuel. A C8-C16 distribution
may be targeted for further processing into a kerosene-type jet fuel. A
C8-C25 distribution may be targeted for further processing into
a diesel fuel.

[0179] The olefins 32, 42, 44 and/or 46 may be oligomerized or polymerized
to form poly-alpha-olefins (PAOs) and/or poly-internal-olefins (PIOs).
The oligomerization or polymerization reaction may be conducted
downstream of the separation unit 30 or downstream of the separation unit
40. Byproducts from the oligomerization or polymerization reactions may
be recycled back to the metathesis reactor 20 for further processing.

[0180] The carboxylic acids and/or esters 34 from the separation unit 30
may be withdrawn as product stream 36 and processed further or sold for
their own value. These acids and/or esters may be used as the
functionalized monomers in accordance with the present invention. Based
upon the quality of separation between olefins 32 and acids and/or esters
34, the acid and/or esters 34 may contain some heavier olefin components
carried over with the functionalized olefins. The acids and/or esters 34
may be polymerized, copolymerized or functionalized in accordance with
the invention. The acids and/or esters 34 may be further processed in a
biorefinery or another chemical or fuel processing unit, thereby
producing various products such as biofuels (e.g., biodiesel) or
specialty chemicals. The acids and/or esters 34 may be partially
withdrawn from the system and sold, with the remainder further processed
in the biorefinery or chemical or fuel processing unit.

[0181] The carboxylic acid and/or ester stream 34 may be advanced to
transesterification unit 70. In the transesterification unit 70, the
esters may be transesterified with one or more alcohols 38 in the
presence of a transesterification catalyst. The alcohol may comprise
methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol,
isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, amyl
alcohol, tert-pentanol, cyclopentanol, cyclohexanol, allyl alcohol,
crotyl alcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethyl
alcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol,
cinnamyl alcohol, or a mixture of two or more thereof. The
transesterification reaction may be conducted at any suitable
temperature, for example, in the range from about 60 to about 70°
C., and at a suitable pressure, for example, atmospheric pressure. The
transesterification catalyst may comprise a homogeneous sodium methoxide
catalyst. Varying amounts of catalyst may be used in the reaction. The
transesterification catalyst may be used at a concentration of about 0.5
to about 1% by weight based on the weight of the esters.

[0182] The transesterification reaction may be used to produce
transesterified products 72, which may include saturated and/or
unsaturated fatty acid methyl esters (FAME), glycerin, methanol, and/or
free fatty acids. The transesterified products 72, or a fraction thereof,
may be used as a middle distillate fuel such as biodiesel. The
transesterified products 72 may comprise 9DA esters, 10UDA esters, 9DDA
esters, and/or 9ODDA esters. Examples of the 9DA esters, 10UDA esters,
9DDA esters, and 9ODDA esters may include methyl 9-decenoate ("9-DAME"),
methyl 10-undecenoate ("10-UDAME"), methyl 9-dodecenoate ("9-DDAME"),
methyl 9-octadecenoate ("9-ODDAME"), respectively. The esters may include
ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- and/or
pentaerythritol esters of 9DA, 10UDA, 9DDA and/or 9ODDA, mixtures of two
or more thereof, and the like. In the transesterification reaction, a 9DA
moiety of a metathesized glyceride may be removed from the glycerol
backbone to form a 9DA ester.

[0183] In an embodiment, glycerol may be used in the transesterification
reaction with a glyceride stream. This reaction may be used to produce
monoglycerides and/or diglycerides.

[0184] The transesterified products 72 from the transesterification unit
70 may be advanced to a liquid-liquid separation unit, wherein the
transesterified products 72 (e.g., fatty acid esters, free fatty acids,
and/or alcohols) may be separated from glycerin. In an embodiment, the
glycerin byproduct stream may be further processed in a secondary
separation unit, wherein the glycerin may be removed and any remaining
alcohols may be recycled back to the transesterification unit 70 for
further processing.

[0185] In an embodiment, the transesterified products 72 may be further
processed in a water-washing unit. In this unit, the transesterified
products may undergo a liquid-liquid extraction when washed with water.
Excess alcohol, water, and glycerin may be removed from the
transesterified products 72. In another embodiment, the water-washing
step may be followed by a drying unit in which excess water may be
removed from the desired mixture of esters which may be used as specialty
chemicals. These specialty chemicals may include, for example, 9DA,
10UDA, 9DDA and/or 9ODDA.

[0186] The transesterified products 72 from the transesterification unit
70 or specialty chemicals from the water-washing unit or drying unit may
be advanced to ester distillation column 80 for further separation of
various individual or groups of compounds. This separation may be used to
provide for the separation of 9DA esters, 10UDA esters, 9DDA esters
and/or 9ODDA esters. In an embodiment, 9DA ester 82 may be distilled or
individually separated from the remaining mixture 84 of transesterified
products or specialty chemicals. The 9DA ester 82 may be the lightest
component in the transesterified product or specialty chemical stream,
and may come out at the top of the ester distillation column 80. In an
embodiment, the remaining mixture 84, or heavier components, of the
transesterified products or specialty chemicals may be separated at the
bottom end of the distillation column 80. This bottoms stream 84 may be
used as a middle distillate fuel such as biodiesel.

[0187] The 9DA esters, 10UDA esters, 9DDA esters and/or 9ODDA esters may
be further processed after the distillation step in the ester
distillation column 80 and/or used as a source of the functionalized
monomer in accordance with the present invention. In an embodiment, the
9DA ester, 10UDA ester, 9DDA ester and/or 9ODDA may undergo a hydrolysis
reaction with water to form 9DA, 10UDA, 9DDA and/or 9ODDA.

[0188] In an embodiment, the fatty acid esters from the transesterified
products 72 may be reacted with each other to form other specialty
chemicals such as dimers.

Hydrogenation of the Metathesis Reactants

[0189] The metathesis reaction involves the interchange of alkylidene
units among olefinic hydrocarbons via the formation and cleavage of
carbon-carbon double bonds. The multiple unsaturated bonds within a
polyunsaturated reactant provide multiple reaction sites for metathesis.
Multiple reaction sites may exponentially increase the chemical identity
of metathesis reaction products, which in turn may increase the
complexity of the metathesis product composition. Multiple reaction sites
within the starting material or reactant may also increase the catalyst
demand for the reaction. These factors may increase the overall
complexity and inefficiency of the metathesis reaction.

[0190] A more efficient metathesis process that can reduce catalyst demand
and reduce complexity of the reaction product composition may be provided
by at least partially hydrogenating the polyunsaturated reactants in the
starting material prior to conducting the metathesis process. This
process step can be used to reduce the polyunsaturated groups within the
starting material. The at least partially hydrogenated reactant may then
be subjected to metathesis to provide a product comprising a mixture of
metathesis products. In some embodiments, the metathesis products are
fatty esters (monoesters or polyol esters) having terminal carbon-carbon
double bonds. The fatty esters may be hydrolyzed to yield linear fatty
acids having terminal carbon-carbon double bonds. In some embodiments,
the linear fatty acids with terminal carbon-carbon double bonds are
monounsaturated. In some embodiments, the terminal linear fatty acids
have a chain length in the range of 3 to n carbon atoms (where n is the
chain length of the at least partially hydrogenated composition which has
a double bond at the 2 to (n-1) position after partial hydrogenation). In
other embodiments, the terminal fatty acids have a chain length in the
range of 5 to (n-1) carbon atoms (where n is the chain length of the at
least partially hydrogenated composition which has a double bond at the 4
to (n-2) position after partial hydrogenation). In exemplary embodiments,
the terminal fatty acids have a chain length in the range of about 5 to
about 17 carbon atoms. In other aspects, the metathesis products are
monounsaturated diesters having a chain length in the range of about 4 to
(2n-2) carbon atoms (where n is the chain length of the at least
partially hydrogenated composition, which has a double bond at the 2 to
(n-1) position after partial hydrogenation). In other embodiments, the
monounsaturated diesters have a chain length in the range of about 8 to
(2n-4) carbon atoms (where n is the chain length of the at least
partially hydrogenated composition which has a double bond at the 4 to
(n-2) position after partial hydrogenation). In exemplary embodiments,
the monounsaturated diesters may have a chain length in the range of
about 8 to about 32 carbon atoms.

[0191] The polyunsaturated starting materials may be at least partially
hydrogenated under conditions to optimize the starting composition for
metathesis. Partial hydrogenation may be used to reduce the number of
double bonds that are available to participate in the metathesis
reaction.

[0192] Partial hydrogenation can also alter the fatty acid composition of
the polyunsaturated fatty acid starting materials or reactants.
Positional and/or geometrical isomerization can occur during
hydrogenation, thus changing the location and/or orientation of the
double bonds. These reactions may occur concurrently. In the geometrical
isomers, the cis bonds originally present in naturally occurring soybean
oil may be converted in part to the trans form.

[0193] Partial hydrogenation can be conducted according to any known
method for hydrogenating double bond-containing compounds such as
vegetable oils. Catalysts for hydrogenation are known and can be
homogeneous or heterogeneous (e.g., present in a different phase,
typically the solid phase, than the substrate). A useful hydrogenation
catalyst is nickel. Other useful hydrogenation catalysts include copper,
palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium,
iridium, zinc or cobalt. Combinations of catalysts can also be used.
Bimetallic catalysts can be used, for example, palladium-copper,
palladium-lead, nickel-chromite.

[0194] The metal catalysts can be utilized with promoters that may or may
not be other metals. Illustrative metal catalysts with promoter include,
for example, nickel with sulfur or copper as promoter; copper with
chromium or zinc as promoter; zinc with chromium as promoter; or
palladium on carbon with silver or bismuth as promoter.

[0195] The polyunsaturated starting composition may be at least partially
hydrogenated in the presence of a nickel catalyst that has been
chemically reduced with hydrogen to an active state. Commercial examples
of supported nickel hydrogenation catalysts may include those available
under the trade designations "NYSOFACT," "NYSOSEL," and "NI 5248 D" (from
Engelhard Corporation, Iselin, N.J.). Additional supported nickel
hydrogenation catalysts may include those commercially available under
the trade designations "PRICAT 9910," "PRICAT 9920," "PRICAT 9908" and
"PRICAT 9936" (from Johnson Matthey Catalysts, Ward Hill, Mass.).

[0196] The metal catalysts can be in the form of fine dispersions in a
hydrogenation reaction (slurry phase environment). For example, in some
embodiments, the particles of supported nickel catalyst may be dispersed
in a protective medium comprising hardened triacylglyceride, edible oil,
or tallow. In an exemplary embodiment, the supported nickel catalyst may
be dispersed in the protective medium at a level of about 22 wt % nickel.

[0197] The catalysts may be impregnated on solid supports. Some useful
supports include carbon, silica, alumina, magnesia, titania, and
zirconia, for example. Illustrative support embodiments include, for
example, palladium, platinum, rhodium or ruthenium on carbon or alumina
support; nickel on magnesia, alumina or zirconia support; palladium on
barium sulfate (BaSO4) support; or copper on silica support.

[0198] The catalysts may be supported nickel or sponge nickel type
catalysts. The hydrogenation catalyst may comprise nickel that has been
chemically reduced with hydrogen to an active state (i.e., reduced
nickel) provided on a support. The support may comprise porous silica
(e.g., kieselguhr, infusorial, diatomaceous, or siliceous earth) or
alumina. The catalysts may be characterized by a high nickel surface area
per gram of nickel.

[0199] The supported nickel catalysts may be of the type reported in U.S.
Pat. No. 3,351,566, the teachings of which are incorporated by reference.
These catalysts comprise solid nickel-silica having a stabilized high
nickel surface area of 45 to 60 sq. meters per gram and a total surface
area of 225 to 300 sq. meters per gram. The catalysts are prepared by
precipitating the nickel and silicate ions from solution such as nickel
hydrosilicate onto porous silica particles in such proportions that the
activated catalyst contains 25 wt % to 50 wt % nickel and a total silica
content of 30 wt % to 90 wt %. The particles are activated by calcining
in air at 600° F. to 900° F. (315.5° C. to
482.2° C.), then reducing with hydrogen.

[0200] Useful catalysts having a high nickel content may include those
described in EP 0 168 091. A soluble aluminum compound is added to the
slurry of the precipitated nickel compound while the precipitate is
maturing. After reduction of the resultant catalyst precursor, the
reduced catalyst typically has a nickel surface area on the order of 90
to 150 sq. meters per gram of total nickel. The catalysts have a
nickel/aluminum atomic ratio in the range of 2 to 10 and have a total
nickel content of more than about 66% by weight.

[0201] Useful high activity nickel/alumina/silica catalysts may include
those described in EP 0 167 201. The reduced catalysts have a high nickel
surface area per gram of total nickel in the catalyst.

[0202] Useful nickel/silica hydrogenation catalysts may include those
described in U.S. Pat. No. 6,846,772, the teachings of which are
incorporated by reference. The catalysts are produced by heating a slurry
of particulate silica (e.g., kieselguhr) in an aqueous nickel amine
carbonate solution for a total period of at least 200 minutes at a pH
above 7.5, followed by filtration, washing, drying, and optionally
calcination. The nickel/silica hydrogenation catalysts are reported to
have improved filtration properties. U.S. Pat. No. 4,490,480 reports high
surface area nickel/alumina hydrogenation catalysts having a total nickel
content of 5% to 40% by weight.

[0203] The amount of hydrogenation catalysts may be selected in view of a
number of factors including, for example, the type of hydrogenation
catalyst(s) used, the degree of unsaturation in the material to be
hydrogenated, the desired rate of hydrogenation, the desired degree of
hydrogenation (for example, as measured by the IV, see below), the purity
of the reagent and the H2 gas pressure. The hydrogenation catalyst
may be used in an amount of about 10 wt % or less, for example about 5 wt
% or less, about 1 wt % or less, or about 0.5 wt % or less.

[0204] Partial hydrogenation may be carried out in a batch, continuous or
semi-continuous process. In a representative batch process, a vacuum is
pulled on the headspace of a stirred reaction vessel and the reaction
vessel is charged with the material to be hydrogenated (for example, RBD
soybean oil). The material is then heated to a desired temperature,
typically in the range of about 50° C. to about 350° C.,
for example, about 100° C. to about 300° C., or about
150° C. to about 250° C. The desired temperature can vary,
for example, with hydrogen gas pressure. Typically, a higher gas pressure
will require a lower temperature. In a separate container, the
hydrogenation catalyst is weighed into a mixing vessel and is slurried in
a small amount of the material to be hydrogenated (for example, RBD
soybean oil). When the material to be hydrogenated reaches the desired
temperature (typically a temperature below a target hydrogenation
temperature), the slurry of hydrogenation catalyst is added to the
reaction vessel. Hydrogen is then pumped into the reaction vessel to
achieve a desired pressure of H2 gas. Typically, the H2 gas
pressure ranges from about 15 psig (103.4 kilopascals) to about 3000 psig
(20684.3 kilopascals), for example, about 15 psig (103.4 kilopascals) to
about 90 psig (620.5 kilopascals). As the gas pressure increases, more
specialized high-pressure processing equipment can be required. Under
these conditions the hydrogenation reaction begins and the temperature is
allowed to increase to the desired hydrogenation temperature (for
example, about 120° C. to about 200° C.), where it is
maintained by cooling the reaction mass, for example, with cooling coils.
When the desired degree of hydrogenation is reached, the reaction mass is
cooled to the desired filtration temperature.

[0205] The polyunsaturated starting materials or reactants for the
metathesis reaction process may be subjected to electrocatalytic
hydrogenation to achieve an at least partially hydrogenated product.
Various electrocatalytic hydrogenation processes can be utilized. For
example, low temperature electrocatalytic hydrogenation that uses an
electrically conducting catalyst such as Raney Nickel or Platinum black
as a cathode are described in Yusem and Pintauro, J. Appl. Electrochem.
1997, 27, 1157-71. Another system that utilizes a solid polymer
electrolyte reactor composed of a ruthenium oxide (RuO2) powder
anode and a platinum-black (Pt-black) or palladium-black (Pd-black)
powder cathode that are hot-pressed as thin films onto a Nafion cation
exchange membrane is described in An et al. J. Am. Oil Chem. Soc. 1998,
75, 917-25. A further system that involves electrochemical hydrogenation
using a hydrogen transfer agent of formic acid and a nickel catalyst is
described in Mondal and Lalvani, J. Am. Oil Chem. Soc. 2003, 80, 1135-41.

[0206] Hydrogenation may be performed under supercritical fluid state, as
described in U.S. Pat. Nos. 5,962,711 and 6,265,596, the teachings of
which are incorporated by reference.

[0207] Hydrogenation may be conducted in a manner to promote selectivity
toward monounsaturated fatty acid groups, i.e., fatty acid groups
containing a single carbon-carbon double bond. Selectivity is understood
here as the tendency of the hydrogenation process to hydrogenate
polyunsaturated fatty acid groups over monounsaturated fatty acid groups.
This form of selectivity is often called preferential selectivity, or
selective hydrogenation.

[0208] The level of selectivity of hydrogenation may be influenced by the
nature of the catalyst, the reaction conditions, and the presence of
impurities. Generally speaking, catalysts having a high selectivity for
one fat or oil reactant may also have a high selectivity in other fat or
oil reactants. As used herein, "selective hydrogenation" refers to
hydrogenation conditions (e.g., selection of catalyst, reaction
conditions such as temperature, rate of heating and/or cooling, catalyst
concentration, hydrogen availability, and the like) that are chosen to
promote hydrogenation of polyunsaturated compounds to monounsaturated
compounds. Using soybean oil as an example, the selectivity of the
hydrogenation process is determined by examining the content of the
various C18 fatty acids and their ratios. Hydrogenation on a macro
scale can be regarded as a stepwise process:

##STR00001##

[0209] The following selectivity ratios (SR) can be defined:
SRI=k2/k3; SRII=k3/k2; SRIII=k2/k1.
Characteristics of the starting oil and the hydrogenated product may be
utilized to determine the selectivity ratio (SR) for each acid. This may
be done with the assistance of gas-liquid chromatography. For example,
polyol esters may be saponified to yield free fatty acids (FFA) by
reacting with NaOH/MeOH. The FFAs may then be methylated into fatty acid
methyl esters (FAMEs) using BF3/MeOH as the acid catalyst and MeOH
as the derivatization reagent. The resulting FAMEs may then be separated
using a gas-liquid chromatograph and are detected with a flame ionization
detector (GC/FID). An internal standard may be used to determine the
weight percent of the fatty esters. The rate constants may be calculated
by either the use of a computer or graph.

[0210] In addition to the selectivity ratios, the following individual
reaction rate constants may be described within the hydrogenation
reaction: k3 (C18:3 to C18:2), k2 (C18:2 to C18:1), and k1
(C18:1 to C18:0). In some aspects, hydrogenation under conditions
sufficient to provide a selectivity or preference for k2 and/or
k3 (i.e., k2 and/or k3 are greater than k1) may be
used. In these aspects, hydrogenation may be conducted to reduce levels
of polyunsaturated compounds within the starting material or reactants
for the metathesis reaction process, while minimizing the generation of
saturated compounds.

[0211] In one illustrative embodiment, selective hydrogenation can promote
hydrogenation of polyunsaturated fatty acid groups toward monounsaturated
fatty acid groups (having one carbon-carbon double bond), for example,
tri- or diunsaturated fatty acid groups to monounsaturated groups. In
some embodiments, the invention involves selective hydrogenation of a
polyunsaturated polyol ester (such as soybean oil) to a hydrogenation
product having a minimum of 65% monounsaturated fatty acid groups, or a
minimum of 75% monounsaturated fatty acid groups, or a minimum of 85%
monounsaturated fatty acid groups. The target minimum percentage of
monounsaturated fatty acid groups will depend upon the starting
composition (i.e., the polyunsaturated polyol ester), since each polyol
ester will have different starting levels of saturates, monounsaturates
and polyunsaturates. It is also understood that high oleic oils can have
80% or more oleic acid. In such cases, very little hydrogenation will be
required to reduce polyunsaturates.

[0212] In one illustrative embodiment, selective hydrogenation can promote
hydrogenation of polyunsaturated fatty acid groups in soybean oil toward
C18:1, for example, C18:2 to C18:1, and/or C18:3 to C18:2. Selective
hydrogenation of a polyunsaturated composition (e.g., a polyol ester such
as soybean oil) to a hydrogenation product may have reduced
polyunsaturated fatty acid group content, while minimizing complete
hydrogenation to saturated fatty acid groups (C18:0).

[0213] Selective hydrogenation may be accomplished by controlling reaction
conditions (such as temperature, rate of heating and/or cooling, hydrogen
availability, and catalyst concentration), and/or by selection of
catalyst. For some hydrogenation catalysts, increased temperature or
catalyst concentration will result in an increased selectivity for
hydrogenating C18:2 over C18:1. In some aspects, when a nickel-supported
catalyst is utilized, pressure and/or temperature can be modified to
provide selectivity. Illustrative lower pressures can include pressures
of 50 psi or less. Lower pressures can be combined, in some embodiments,
with increased temperature to promote selectivity. Illustrative
conditions in accordance with these embodiments include temperatures in
the range of 180° C. to 220° C., pressure of about 5 psi,
with nickel catalyst present in an amount of about 0.5 wt %. See, for
example, Allen et al. "Isomerization During Hydrogenation. III. Linoleic
Acid," JAOC August 1956.

[0214] In some aspects, selectivity can be enhanced by diminishing the
availability of hydrogen. For example, reduced reaction pressure and/or
agitation rate can diminish hydrogen supply for the reaction.

[0215] Selective hydrogenation can be accomplished by selection of the
catalyst. One illustrative catalyst that can enhance selectivity is
palladium. Palladium reaction conditions for sunflower seed oil can
include low temperatures (e.g., 40° C.) in ethanol solvent, with
catalyst present in an amount of about 1 wt %. Palladium can be provided
on a variety of different supports known for hydrogenation processes.
See, for example, Bendaoud Nohaira et al., Palladium supported catalysts
for the selective hydrogenation of sunflower oil," J. of Molecular
Catalysts A: Chemical 229 (2005) 117-126, Nov. 20, 2004.

[0216] Optionally, additives such as lead or copper can be included to
increase selectivity. When catalysts containing palladium, nickel or
cobalt are used, additives such as amines can be used.

[0217] Useful selective hydrogenation conditions are described, for
example, in U.S. Pat. Nos. 5,962,711 and 6,265,596, the teachings of
which are incorporated by reference. Hydrogenation is performed by mixing
the substrate (polyunsaturated polyol ester), hydrogen gas and solvent,
and bringing the whole mixture into a super-critical or near-critical
state. This substantially homogeneous super-critical or near-critical
solution is led over the catalyst, whereby the reaction products formed
(i.e., the hydrogenated substrates) will also be a part of the
substantially homogeneous super-critical or near-critical solution.

[0218] Reaction conditions for supercritical hydrogenation may occur over
a wide experimental range, and this range can be described as follows:
temperature (in the range of about 0° C. to about 250° C.,
or about 20° C. to about 200° C.); pressure (in the range
of about 1000 to about 35,000 kilopascals, or about 2000 to about 20,000
kilopascals); reaction time (up to about 10 minutes, or in the range of
about 1 second to about 1 minute); and solvent concentration (in the
range of about 30 wt % to about 99.9 wt %, or about 40 wt % to about 99
wt %). Useful solvents include, for example, ethane, propane, butane,
CO2, dimethyl ether, "freons," N2O, N2, NH3, or
mixtures of these. The catalyst can be selected according to the reaction
to be carried out; any useful catalyst for hydrogenation can be selected.
Concentration of hydrogen gas (H2) can be up to 3 wt %, or in the
range of about 0.001 wt % to about 1 wt %. Concentration of substrate
(polyunsaturated polyol ester) in the reaction mixture can be in the
range of about 0.1 wt % to about 70 wt %, or about 1 wt % to about 60 wt
%. A continuous reactor can be used to conduct the hydrogenation
reaction, such as described in U.S. Pat. Nos. 5,962,711 and 6,265,596,
the teachings of which are incorporated by reference.

[0219] The content of the starting material may influence the selectivity.
Various substances that are naturally occurring in fats and oils may
influence the selectivity of hydrogenation. For example, sulfur is known
to be an irreversible surface poison for nickel catalysts. Other
compounds that may inhibit catalyst activity include phosphatides,
nitrogen and halogen derivatives. As a result, a refining step to remove
substances that may have a net negative impact on the hydrogenation
process may be used. This, in turn, may increase selectivity.

[0220] Products of the partial hydrogenation reaction can include one or
more identifiable properties and/or compounds. Products formed from
polyunsaturated compositions can include characteristic monounsaturated
fatty acid groups in an acid profile and can contain minor amounts of
polyunsaturated fatty acid groups. In some aspects, the acid profile
comprises polyunsaturated fatty acid groups in an amount of about 1 wt %
or less. In some aspects, the starting material is soybean oil, and the
acid profile of the hydrogenation product comprises a majority of
monounsaturated fatty acid groups having a carbon-carbon double bond in
the C4 to C16 position on the fatty acid or ester. More
generally speaking, the carbon-carbon double bond is located on the fatty
acid or ester in the C2 to C(n-1) position, where n is the chain
length of the fatty acid or ester. More typically, the carbon-carbon
double bond is located on the fatty acid or ester in the C4 to
C(n-2), where n is the chain length of the fatty acid or ester.
Typically, n ranges from about 4 to about 30, or from about 4 to about
22.

[0221] When the starting material is derived from soybean oil, the acid
profile of the partial hydrogenation product composition may comprise
saturated fatty acid groups in an amount that is slightly higher than the
starting concentration of saturated fatty acid groups in the starting
material (i.e., unhydrogenated polyunsaturated polyol ester). The acid
profile of the partial hydrogenation product composition may comprise
saturated fatty acid groups in an amount of about 0.5 wt % to about 10 wt
% higher than the concentration of saturated fatty acid groups in the
starting material (polyunsaturated polyol ester starting material). The
acid profile of the partial hydrogenation product composition may
comprise saturated fatty acid groups in an amount of about 0.5 wt % to
about 6 wt % higher than the concentration of saturated fatty acid groups
in the starting material. It is understood that partial hydrogenation may
result in generation of some additional saturated fatty acid groups. The
generation of such additional saturated fatty acid groups may be
controlled through selectivity. Generally speaking, saturated fatty acid
groups do not participate in a subsequent metathesis reaction and thus
can represent yield loss.

[0222] As one example of a partial hydrogenation product composition, when
the starting material comprises soybean oil, a partial hydrogenation
product composition may include saturated fatty acid groups in an amount
of about 30 wt % or less, or 25 wt % or less, or 20 wt % or less. The
acid profile may comprise saturated fatty acid groups in an amount in the
range of about 15 wt % to about 20 wt %. For soybean oil, illustrative
saturated fatty acid groups may include stearic and palmitic acids. It is
understood the relative amount and identity of the saturated fatty acids
within the at least partial hydrogenated product composition can vary,
depending upon such factors as the starting material (polyunsaturated
polyol ester), reaction conditions (including catalyst, temperature,
pressure, and other factors impacting selectivity of hydrogenation), and
positional isomerization. A representative example of a hydrogenation
product from selective hydrogenation of soybean oil (SBO) is shown in
Table C below.

[0239] An objective of selective hydrogenation is reduction in the amount
of polyunsaturated fatty acid groups of the polyunsaturated composition
(e.g., polyunsaturated polyol ester). The hydrogenation product
composition may have a polyunsaturated fatty acid group content of about
10 wt % or less, based upon total fatty acid content in the composition.
Particularly with respect to the hydrogenation product that is to be
subjected to self-metathesis, hydrogenation can, be performed to drive
down the concentration of polyunsaturated fatty acid groups even lower
than about 5 wt %, for example to concentrations of about 1 wt % or less,
or about 0.75 wt % or less, or about 0.5 wt % or less.

[0240] The hydrogenation product composition thus may comprise a reduced
polyunsaturate content relative to the polyunsaturated starting material.
The hydrogenation product composition may comprise polyunsaturated fatty
acid groups in an amount of about 1 wt % or less; saturated fatty acid
groups in an amount in the range of about 30 wt % or less, or about 25 wt
% or less, or about 20 wt % or less; and monounsaturated fatty acid
groups comprising the balance of the mixture, for example, about 65 wt %
or more, or about 70 wt % or more, or about 75 wt % or more, or about 80
wt % or more, or about 85 wt % or more. This product composition is
understood to be illustrative for soybean oil, and it is understood that
the relative amounts of each level of saturated, monounsaturated and
polyunsaturated components could vary depending upon such factors as the
starting material (e.g., polyunsaturated polyol ester), the hydrogenation
catalyst selected, the hydrogenation reaction conditions, and the like
factors described herein.

[0241] It may be desirable to maximize the concentration of
monounsaturated fatty acid groups in the hydrogenation product
composition. In many embodiments, the monounsaturated fatty acid groups
may comprise monounsaturated fatty acid groups having the carbon-carbon
double bond in the C4 to C16 position within the carbon chain.

[0242] The hydrogenation product composition thus may comprise a partially
hydrogenated polyol ester. As mentioned previously, in addition to
effecting a reduction of unsaturation of the polyol ester, partial
hydrogenation can also cause geometric and positional isomers to be
formed. A goal of selective hydrogenation may be reduction in the amount
of polyunsaturation in the polyol esters.

[0243] The hydrogenation product composition can also be characterized as
having an iodine number within a desired range. The iodine number is a
measure of the degree of unsaturation of a compound. When used in
reference to an unsaturated material, such as an unsaturated polyol
ester, the iodine number is a measure of the unsaturation, or the number
of double bonds, of that compound or mixture.

[0244] Generally speaking, the iodine number may range from about 8 to
about 180 in naturally-occurring seed oils, and from about 90 to about
210 in naturally-occurring marine oils. Illustrative iodine numbers for
some natural oils are the following:

[0245] At complete hydrogenation of oils or fats, all double bonds would
be hydrogenated and the iodine number would therefore be zero or near
zero. For partially hydrogenated triglycerides the iodine number may be
about 90 or lower, or about 85 or lower, or about 80 or lower, or about
75 or lower. The iodine number target will depend upon such factors as
the initial iodine number, the content of the monounsaturates in the
starting material, the selectivity of the hydrogenation catalyst, the
economic optimum level of unsaturation, and the like. An optimum partial
hydrogenation would leave only the saturates that were initially present
in the polyunsaturated polyol ester starting material and react all of
the polyunsaturates. For example, a triolein oil would have an iodine
number of about 86. Soybean oil starts with an iodine number of around
130 with a saturates content of about 15%. An optimum partial
hydrogenation product may have an iodine number of about 73 and would
maintain the 15% level of saturates. Canola oil has an initial iodine
number of about 113 and 7% saturates; an optimum partial hydrogenation
product may have an iodine number of about 80, while maintaining the 7%
saturate level. The balance between additional saturate production and
allowable polyunsaturate content may depend upon such factors as product
quality parameters, yield costs, catalyst costs, and the like. If
catalyst costs dominate, then some saturate production may be tolerable.
If yield is critical, then some remaining polyunsaturates may be
tolerable. If the formation of cyclic byproducts is unacceptable, then it
may be acceptable to drive polyunsaturate levels to near zero.

[0246] The iodine number may represent a hydrogenation product composition
wherein a certain percentage of double bonds have reacted, on a molar
basis, based upon the starting iodine number of the polyunsaturated
composition. For example, soybean oil with an iodine number of about 130
may be used as the starting material for the metathesis reaction process.

[0247] After at least partial hydrogenation, the hydrogenation catalyst
may be removed from the partial hydrogenated product using known
techniques, for example, by filtration. The hydrogenation catalyst may be
removed using a plate and frame filter such as those commercially
available from Sparkle Filters, Inc., Conroe, Tex. The filtration may be
performed with the assistance of pressure or a vacuum. In order to
improve filtering performance, a filter aid can optionally be used. A
filter aid can be added to the hydrogenated product directly or it can be
applied to the filter. Representative examples of filtering aids include
diatomaceous earth, silica, alumina and carbon. Typically, the filtering
aid is used in an amount of about 10 wt % or less, for example, about 5
wt % or less, or about 1 wt % or less. Other filtering techniques and
filtering aids can also be employed to remove the used hydrogenation
catalyst. In other embodiments, the hydrogenation catalyst is removed by
using centrifugation followed by decantation of the product.

[0248] Partial hydrogenation of a polyunsaturated composition can impart
one or more desirable properties to the at least partially hydrogenated
composition and, consequently, to metathesis processes performed on the
at least partially hydrogenated composition. For example, partial
hydrogenation can be used to decrease the amount of polyunsaturated fatty
acid groups in the composition, thereby reducing unneeded sites of
reaction for a metathesis catalyst. This, in turn, can reduce catalyst
demand. Another benefit can be seen in the final metathesis product
composition. Because less polyunsaturated fatty acid groups are present
in the reaction mixture prior to metathesis, a more predictable
metathesis product composition can be provided. For example, the carbon
chain length and double bond position of metathesis products can be
predicted, based upon the fatty acid composition and metathesis catalyst
utilized. This, in turn, can reduce the purification requirements for the
metathesis product composition.

The Metathesis Catalyst

[0249] The metathesis reaction may be conducted in the presence of a
catalytically effective amount of a metathesis catalyst. The term
"metathesis catalyst" includes any catalyst or catalyst system which
catalyzes the metathesis reaction.

[0250] The metathesis catalyst may be used, alone or in combination with
one or more additional catalysts. Exemplary metathesis catalysts may
include metal carbene catalysts based upon transition metals, for
example, ruthenium, molybdenum, osmium, chromium, rhenium, and/or
tungsten. The metathesis catalyst may be a metal complex having the
structure of the following formula (I)

##STR00002##

[0251] in which the various substituents are as follows: [0252] M is
ruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten. [0253]
L1, L2 and L3 are neutral electron donor ligands; [0254] n
is 0 or 1, such that L3 may or may not be present; [0255] m is 0, 1,
or 2; [0256] X1 and X2 are anionic ligands; and

[0258] wherein any two or more of X1, X2, L1, L2,
L3, R1, and R2 can be taken together to form a cyclic
group, and further wherein any one or more of X1, X2, L1,
L2, L3, R1, and R2 may be attached to a support.

[0260] Numerous embodiments of the catalysts useful in the reactions of
the disclosure are described in more detail infra. For the sake of
convenience, the catalysts are described in groups, but it should be
emphasized that these groups are not meant to be limiting in any way.
That is, any of the catalysts useful in the disclosure may fit the
description of more than one of the groups described herein.

[0261] A first group of catalysts, which may be referred to as 1st
Generation Grubbs-type catalysts, have the structure of formula (I). For
the first group of catalysts, M and m are as described above, and n,
X1, X2, L2, L3, R1, and R2 are described as
follows.

[0263] X1 and X2 may be anionic ligands, and may be the same or
different, or may be linked together to form a cyclic group which may be
a five- to eight-membered ring. X1 and X2 may each be
independently hydrogen, halide, or one of the following groups:
C1-C20 alkyl, C5-C24 aryl, C1-C20 alkoxy,
C5-C24 aryloxy, C2-C20 alkoxycarbonyl,
C6-C24 aryloxycarbonyl, C2-C24 acyl, C2-C24
acyloxy, C1-C20 alkylsulfonato, C5-C24 arylsulfonato,
C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl,
C1-C20 alkylsulfinyl, or C5-C24 arylsulfinyl. X1
and X2 may be substituted with one or more moieties selected from
C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl,
and halide, which may, in turn, with the exception of halide, be further
substituted with one or more groups selected from halide, C1-C6
alkyl, C1-C6 alkoxy, and phenyl. X1 and X2 may be
halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl,
C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6
alkylsulfanyl, aryl, or C1-C6 alkylsulfonyl. X1 and
X2 may each be halide, CF3CO2, CH3CO2,
CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO,
(CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or
trifluoromethane-sulfonate. X1 and X2 may each be chloride.

[0265] R1 may be hydrogen and R2 may be selected from
C1-C20 alkyl, C2-C20 alkenyl, C5-C24 aryl,
C1-C6 alkyl, C2-C6 alkenyl, or C5-C14 aryl.
R2 may be phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally
substituted with one or more moieties selected from C1-C6
alkyl, C1-C6 alkoxy, phenyl, or a functional group. R2 may
be phenyl or vinyl substituted with one or more moieties selected from
methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl,
methoxy, and phenyl. R2 may be phenyl or --C═C(CH3)2.

[0266] Any two or more (typically two, three, or four) of X1,
X2, L1, L2, L3, R1, and R2 can be taken
together to form a cyclic group, as disclosed, for example, in U.S. Pat.
No. 5,312,940, the teachings of which are incorporated by reference. When
any of X1, X2, L1, L2, L3, R1, and R2
are linked to form cyclic groups, those cyclic groups may contain 4 to
about 12, or 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such
rings, which may be either fused or linked. The cyclic groups may be
aliphatic or aromatic, and may be heteroatom-containing and/or
substituted. The cyclic group may form a bidentate ligand or a tridentate
ligand. Examples of bidentate ligands may include bisphosphines,
dialkoxides, alkyldiketonates, and aryldiketonates.

[0267] A second group of catalysts, which may be referred to as 2nd
Generation Grubbs-type catalysts, have the structure of formula (I),
wherein L1 is a carbene ligand having the structure of formula (II)

##STR00003##

such that the complex may have the structure of formula (III)

##STR00004##

[0268] wherein M, m, n, X1, X2, L1, L2, L3,
R1, and R2 are as defined for the first group of catalysts, and
the remaining substituents are as follows.

[0269] X and Y may be heteroatoms typically selected from N, O, S, and P.
Since O and S are divalent, p is zero when X is O or S, and q is zero
when Y is O or S. When X is N or P, then p is 1, and when Y is N or P,
then q is 1. Both X and Y may be N.

[0270] Q1, Q2, Q3, and Q4 may be linkers, e.g.,
hydrocarbylene (including substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and substituted
heteroatom-containing hydrocarbylene, such as substituted and/or
heteroatom-containing alkylene) or --(CO)--, and w, x, y, and z are
independently zero or 1, meaning that each linker is optional. w, x, y,
and z may all be zero. Two or more substituents on adjacent atoms within
Q1, Q2, Q3, and Q4 may be linked to form an
additional cyclic group.

[0272] In addition, any two or more of X1, X2, L1, L2,
L3, R1, R2, R3, R3A, R4, and R4A can
be taken together to form a cyclic group, and any one or more of X1,
X2, L1, L2, L3, R1, R2, R3, R3A,
R4, and R4A may be attached to a support.

[0273] R3A and R4A may be linked to form a cyclic group so that
the carbene ligand is an heterocyclic carbine, for example, an
N-heterocyclic carbene, such as the N-heterocyclic carbene having the
structure of formula (IV):

##STR00005##

where R3 and R4 are defined above at least one of R3 and
R4, and advantageously both R3 and R4, may be alicyclic or
aromatic of one to about five rings, and optionally containing one or
more heteroatoms and/or substituents. Q may be a linker, typically a
hydrocarbylene linker, including substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and substituted
heteroatom-containing hydrocarbylene linkers, wherein two or more
substituents on adjacent atoms within Q may also be linked to form an
additional cyclic structure, which may be similarly substituted to
provide a fused polycyclic structure of two to about five cyclic groups.
Q may comprise a two-atom linkage or a three-atom linkage.

[0274] Examples of N-heterocyclic carbene ligands suitable as L1 may
include the following:

##STR00006##

When M is ruthenium, the complex may have the structure of formula (V):

##STR00007##

Q may be a two-atom linkage having the structure
--CR11R12--CR13R14-- or --CR11═CR13--,
wherein R11, R12, R13, and R14 are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted heteroatom-containing
hydrocarbyl, and functional groups. Examples of functional groups may
include carboxyl, C1-C20 alkoxy, C5-C24 aryloxy,
C2-C20 alkoxycarbonyl, C5-C24 alkoxycarbonyl,
C2-C24 acyloxy, C1-C20 alkylthio, C5-C24
arylthio, C1-C20 alkylsulfonyl, and C1-C20
alkylsulfinyl, optionally substituted with one or more moieties selected
from C1-C12 alkyl, C1-C12 alkoxy, C5-C14
aryl, hydroxyl, sulfhydryl, formyl, and halide. R11, R12,
R13, and R14 may be independently selected from hydrogen,
C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12
heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and
substituted phenyl. Any two of R11, R12, R13, and R14
may be linked together to form a substituted or unsubstituted, saturated
or unsaturated ring structure, e.g., a C4-C12 alicyclic group
or a C5 or C6 aryl group, which may itself be substituted,
e.g., with linked or fused alicyclic or aromatic groups, or with other
substituents.

[0275] When R3 and R4 are aromatic, they may be composed of one
or two aromatic rings, which may or may not be substituted, e.g., R3
and R4 may be phenyl, substituted phenyl, biphenyl, substituted
biphenyl, or the like. R3 and R4 may be the same and each may
be unsubstituted phenyl or phenyl substituted with up to three
substituents selected from C1-C20 alkyl, substituted
C1-C20 alkyl, C1-C20 heteroalkyl, substituted
C1-C20 heteroalkyl, C5-C24 aryl, substituted
C5-C24 aryl, C5-C24 heteroaryl, C6-C24
aralkyl, C6-C24 alkaryl, or halide. Any substituents present
may be hydrogen, C1-C12 alkyl, C1-C12 alkoxy,
C5-C14 aryl, substituted C5-C14 aryl, or halide. As
an example, R3 and R4 may be mesityl.

[0276] In a third group of catalysts having the structure of formula (I),
M, m, n, X1, X2, R1, and R2 are as defined for the
first group of catalysts, L1 may be a strongly coordinating neutral
electron donor ligand such as any of those described for the first and
second groups of catalysts, and L2 and L3 may be weakly
coordinating neutral electron donor ligands in the form of optionally
substituted heterocyclic groups. n is zero or 1, such that L3 may or
may not be present. In the third group of catalysts, L2 and L3
may be optionally substituted five- or six-membered monocyclic groups
containing 1 to about 4, or 1 to about 3, or 1 to 2 heteroatoms, or are
optionally substituted bicyclic or polycyclic structures composed of 2 to
about 5 such five- or six-membered monocyclic groups. If the heterocyclic
group is substituted, it should not be substituted on a coordinating
heteroatom, and any one cyclic moiety within a heterocyclic group may not
be substituted with more than 3 substituents.

[0277] For the third group of catalysts, examples of L2 and L3
may include, heterocycles containing nitrogen, sulfur, oxygen, or a
mixture thereof.

[0286] L2 and L3 may also be taken together to form a bidentate
or multidentate ligand containing two or more, generally two,
coordinating heteroatoms such as N, O, S, or P. These may include diimine
ligands of the Brookhart type. A representative bidentate ligand has the
structure of formula (VI)

[0287] In a fourth group of catalysts that have the structure of formula
(I), two of the substituents may be taken together to form a bidentate
ligand or a tridentate ligand. Examples of bidentate ligands may include
bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. These
may include --P(Ph)2CH2CH2P(Ph)2-,
--As(Ph)2CH2CH2As(Ph2)-,
--P(Ph)2CH2CH2C(CF3)2O--, binaphtholate
dianions, pinacolate dianions,
--P(CH3)2(CH2)2P(CH3)2--, and
--OC(CH3)2(CH3)2CO--. Preferred bidentate ligands are
--P(Ph)2CH2CH2P(Ph)2- and
--P(CH3)2(CH2)2P(CH3)2--. Tridentate
ligands include, but are not limited to,
(CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2.
Other tridentate ligands may be those in which any three of X1,
X2, L1, L2, L3, R1, and R2 (e.g., X1,
L1, and L2) are taken together to be cyclopentadienyl, indenyl,
or fluorenyl, each optionally substituted with C2-C20 alkenyl,
C2-C20 alkynyl, C1-C20 alkyl, C5-C20 aryl,
C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20
alkynyloxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl,
C1-C20 alkylthio, C1-C20 alkylsulfonyl, or
C1-C20 alkylsulfinyl, each of which may be further substituted
with C1-C6 alkyl, halide, C1-C6 alkoxy or with a
phenyl group optionally substituted with halide, C1-C6 alkyl,
or C1-C6 alkoxy. In compounds of this type, X, L1, and
L2 may be taken together to be cyclopentadienyl or indenyl, each
optionally substituted with vinyl, C1-C10 alkyl,
C5-C20 aryl, C1-C10 carboxylate, C2-C10
alkoxycarbonyl, C1-C10 alkoxy, or C5-C20 aryloxy,
each optionally substituted with C1-C6 alkyl, halide,
C1-C6 alkoxy or with a phenyl group optionally substituted with
halide, C1-C6 alkyl or C1-C6 alkoxy. X, L1 and
L2 may be taken together to be cyclopentadienyl, optionally
substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands
may include
O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.

[0288] Complexes wherein L2 and R2 are linked are examples of
the fourth group of catalysts. These may be called "Grubbs-Hoveyda"
catalysts. Examples of Grubbs-Hoveyda-type catalysts may include the
following:

##STR00009##

[0289] wherein L1, X1, X2, and M are as described for any
of the other groups of catalysts.

[0290] In addition to the catalysts that have the structure of formula
(I), as described above, other transition metal carbene complexes may
include;

[0291] neutral ruthenium or osmium metal carbene complexes containing
metal centers that are formally in the +2 oxidation state, have an
electron count of 16, are penta-coordinated, and are of the general
formula (VII);

[0292] neutral ruthenium or osmium metal carbene complexes containing
metal centers that are formally in the +2 oxidation state, have an
electron count of 18, are hexa-coordinated, and are of the general
formula (VIII);

[0293] cationic ruthenium or osmium metal carbene complexes containing
metal centers that are formally in the +2 oxidation state, have an
electron count of 14, are tetra-coordinated, and are of the general
formula (IX); and

[0294] cationic ruthenium or osmium metal carbene complexes containing
metal centers that are formally in the +2 oxidation state, have an
electron count of 14, are tetra-coordinated, and are of the general
formula (X)

##STR00010##

wherein: X1, X2, L1, L2, n, L3, R1, and
R2 may be as defined for any of the previously defined four groups
of catalysts; r and s are independently zero or 1; t may be an integer in
the range of zero to 5;

[0295] Y may be any non-coordinating anion (e.g., a halide ion,
BF4.sup.-, etc.); Z1 and Z2 may be independently selected
from --O--, --S--, --NR2--, --P(═O)R2--, --P(OR2)--,
--P(═O)(OR2)--, --C(═O)--, --C(═O)O--, --OC(═O)--,
--OC(═O)O--, --S(═O)--, and --S(═O)2--; Z3 may be
any cationic moiety such as --P(R2)3.sup.+ or
--N(R2)3.sup.+; and

[0296] any two or more of X1, X2, L1, L2, L3, n,
Z1, Z2, Z3, R1, and R2 may be taken together to
form a cyclic group, e.g., a multidentate ligand, and

[0297] wherein any one or more of X1, X2, L1, L2, n,
L3, Z1, Z2, Z3, R1, and R2 may be attached
to a support.

[0298] Other suitable complexes include Group 8 transition metal carbenes
bearing a cationic substituent, such as are disclosed in U.S. Pat. No.
7,365,140 (Piers et al.) having the general structure (XI):

[0307] n is zero or 1; [0308] wherein any two or more of L1,
L2, X1, X2, R1, W, and Y can be taken together to
form a cyclic group.

[0309] Each of M, L1, L2, X1, and X2 in structure (XI)
may be as previously defined herein.

[0310] W may be an optionally substituted and/or heteroatom-containing
C1-C20 hydrocarbylene linkage, typically an optionally
substituted C1-C12 alkylene linkage, e.g., --(CH2)i--
where i is an integer in the range of 1 to 12 inclusive and any of the
hydrogen atoms may be replaced with a non-hydrogen substituent as
described earlier herein with regard to the definition of the term
"substituted."The subscript n may be zero or 1, meaning that W may or may
not be present. In an embodiment, n is zero.

[0311] Y may be a positively charged Group 15 or Group 16 element
substituted with hydrogen, C1-C12 hydrocarbyl, substituted
C1-C12 hydrocarbyl, heteroatom-containing C1-C12
hydrocarbyl, or substituted heteroatom-containing hydrocarbyl. Y may be a
C1-C12 hydrocarbyl-substituted, positively charged Group 15 or
Group 16 element. Representative Y groups may include P(R2)3,
P(R2)3, As(R2)3, S(R2)2, O(R2)2,
where the R2 may be independently selected from C1-C12
hydrocarbyl. Within these, the Y groups may be phosphines of the
structure P(R2)3 wherein the R2 may be independently
selected from C1-C12 alkyl and aryl, and thus include, for
example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl,
cyclopentyl, cyclohexyl, and phenyl. Y may also be a heterocyclic group
containing the positively charged Group 15 or Group 16 element. For
instance, when the Group 15 or Group 16 element is nitrogen, Y may be an
optionally substituted pyridinyl, pyrazinyl, or imidazolyl group.

[0312] Z.sup.- may be a negatively charged counterion associated with the
cationic complex, and may be virtually any anion, so long as the anion is
inert with respect to the components of the complex and the reactants and
reagents used in the metathesis reaction. The Z.sup.- moieties may be
weakly coordinating anions, such as, for instance,
[B(C6F5)4].sup.-, [BF4].sup.-,
[B(C6H6)4].sup.-, [CF3S(O)3].sup.-,
[PF6].sup.-, [SbF6].sup.-, [AlCl4].sup.-,
[FSO3].sup.-, [CB11H6Cl6].sup.-,
[CB11H6Br6].sup.-, and [SO3F:SbF5].sup.-. Anions
suitable as Z.sup.- may be of the formula B(R15)4.sup.- where
R15 is fluoro, aryl, or perfluorinated aryl, typically fluoro or
perfluorinated aryl. Anions suitable as Z.sup.- may be BF4.sup.- or
B(C6F5).sup.-.

[0313] Any two or more of X1, X2, L1, L2, R1, W,
and Y may be taken together to form a cyclic group, as disclosed, for
example, in U.S. Pat. No. 5,312,940. When any of X1, X2,
L1, L2, R1, W, and Y are linked to form cyclic groups,
those cyclic groups may be five- or six-membered rings, or may comprise
two or three five- or six-membered rings, which may be either fused or
linked. The cyclic groups may be aliphatic or aromatic, and may be
heteroatom-containing and/or substituted.

[0314] One group of exemplary catalysts encompassed by the structure of
formula (XI) are those wherein m and n are zero, such that the complex
has the structure of formula (XII)

##STR00012##

The X1, X2, and L1 ligands are as described earlier with
respect to complexes of formula (XI), as are Y.sup.+ and Z.sup.-. M may
be Ru or Os and R1 may be hydrogen or C1-C12 alkyl. M may
be Ru, and R1 may be hydrogen.

[0315] In formula (XII)-type catalysts, L1 may be a
heteroatom-containing carbene ligand having the structure of formula
(XIII)

##STR00013##

such that complex (XII) has the structure of formula (XIV)

##STR00014##

wherein X1, X2, R1, R2, Y, and Z are as defined
previously, and the remaining substituents are as follows:

[0316] Z1 and Z2 may be heteroatoms typically selected from N,
O, S, and P. Since O and S are divalent, j may be zero when Z1 is O
or S, and k may be zero when Z2 is O or S. However, when Z1 is
N or P, then j may be 1, and when Z2 is N or P, then k may be 1.
Both Z1 and Z2 may be N.

[0317] Q1, Q2, Q3, and Q4 are linkers, e.g.,
C1-C12 hydrocarbylene, substituted C1-C12
hydrocarbylene, heteroatom-containing C1-C12 hydrocarbylene,
substituted heteroatom-containing C1-C12 hydrocarbylene, or
--(CO)--, and w, x, y, and z may be independently zero or 1, meaning that
each linker may be optional. w, x, y, and z may all be zero.

[0319] w, x, y, and z may be zero, Z1 and Z1 may be N, and
R3A and R4A may be linked to form -Q-, such that the complex
has the structure of formula (XV)

##STR00015##

wherein R3 and R4 are defined above. At least one of R3
and R4, and optionally both R3 and R4, may be alicyclic or
aromatic of one to about five rings, and optionally containing one or
more heteroatoms and/or substituents. Q may be a linker, typically a
hydrocarbylene linker, including C1-C12 hydrocarbylene,
substituted C1-C12 hydrocarbylene, heteroatom-containing
C1-C12 hydrocarbylene, or substituted heteroatom-containing
C1-C12 hydrocarbylene linker, wherein two or more substituents
on adjacent atoms within Q may be linked to form an additional cyclic
structure, which may be similarly substituted to provide a fused
polycyclic structure of two to about five cyclic groups. Q may be a
two-atom linkage or a three-atom linkage, e.g., --CH2--CH2--,
--CH(Ph)-CH(Ph)- where Ph is phenyl; ═CR--N═, giving rise to an
unsubstituted (when R═H) or substituted (R=other than H) triazolyl
group; or --CH2--SiR2--CH2-- (where R is H, alkyl, alkoxy,
etc.).

[0320] Q may be a two-atom linkage having the structure
--CR8R9--CR10R11-- or --CR8═CR10--,
wherein R8, R9, R10, and R11 may be independently
selected from hydrogen, C1-C12 hydrocarbyl, substituted
C1-C12 hydrocarbyl, heteroatom-containing C1-C12
hydrocarbyl, substituted heteroatom-containing C1-C12
hydrocarbyl, and functional groups. Examples of the functional groups may
include carboxyl, C1-C20 alkoxy, C5-C20 aryloxy,
C2-C20 alkoxycarbonyl, C2-C20 alkoxycarbonyl,
C2-C20 acyloxy, C1-C20 alkylthio, C5-C20
arylthio, C1-C20 alkylsulfonyl, and C1-C20
alkylsulfinyl, optionally substituted with one or more moieties selected
from C1-C10 alkyl, C1-C10 alkoxy, C5-C20
aryl, hydroxyl, sulfhydryl, formyl, and halide. Alternatively, any two of
R8, R9, R10, and R11 may be linked together to form a
substituted or unsubstituted, saturated or unsaturated ring structure,
e.g., a C4-C12 alicyclic group or a C5 or C6 aryl
group, which may itself be substituted, e.g., with linked or fused
alicyclic or aromatic groups, or with other substituents.

[0321] Further details concerning such formula (XI) complexes, as well as
associated preparation methods, may be obtained from U.S. Pat. No.
7,365,140, the teachings of which are incorporated by reference.

[0322] Suitable solid supports for any of the catalysts described herein
may be made of synthetic, semi-synthetic, or naturally occurring
materials, which may be organic or inorganic, e.g., polymeric, ceramic,
or metallic. Attachment to the support may be covalent, and the covalent
linkage may be direct or indirect, if indirect, typically through a
functional group on a support surface.

[0323] Examples of the catalysts that may be used may include the
following, some of which for convenience are identified throughout this
disclosure by reference to their molecular weight:

[0327] Techniques for using the metathesis catalysts are known in the art
(see, for example, U.S. Pat. Nos. 7,102,047; 6,794,534; 6,696,597;
6,414,097; 6,306,988; 5,922,863; 5,750,815; and metathesis catalysts with
ligands in U.S. Patent Publication No. 2007/0004917 A1), the teachings of
which are incorporated by reference. A number of the metathesis catalysts
as shown are manufactured by Materia, Inc. (Pasadena, Calif.).

[0328] Additional exemplary metathesis catalysts may include metal carbene
complexes selected from molybdenum, osmium, chromium, rhenium, and
tungsten. The term "complex" refers to a metal atom, such as a transition
metal atom, with at least one ligand or complexing agent coordinated or
bound thereto. Such a ligand may be a Lewis base in metal carbene
complexes useful for alkyne or alkene-metathesis. Typical examples of
such ligands include phosphines, halides and stabilized carbenes. Some
metathesis catalysts may employ plural metals or metal co-catalysts
(e.g., a catalyst comprising a tungsten halide, a tetraalkyl tin
compound, and an organoaluminum compound).

[0329] An immobilized catalyst can be used for the metathesis process. An
immobilized catalyst may be a system comprising a catalyst and a support,
the catalyst associated with the support. Exemplary associations between
the catalyst and the support may occur by way of chemical bonds or weak
interactions (e.g. hydrogen bonds, donor acceptor interactions) between
the catalyst, or any portions thereof, and the support or any portions
thereof. Support may be any material suitable to support the catalyst.
Typically, immobilized catalysts may be solid phase catalysts that act on
liquid or gas phase reactants and products. Exemplary supports may
include polymers, silica or alumina. Such an immobilized catalyst may be
used in a flow process. An immobilized catalyst may simplify purification
of products and recovery of the catalyst so that recycling the catalyst
may be more convenient.

Polymerization of the Functionalized Monomers to Form Functionalized
Polymers

[0330] One or more of the functionalized monomers may be polymerized to
form a functionalized polymer, or copolymerized with one or more
comonomers to form a functionalized copolymer. The term "polymer" is used
herein to refer to both polymers and copolymers. The functionalized
polymers may have utility in many applications including lubricants,
functional fluids, fuels, molded or extruded articles, pharmaceuticals,
cosmetics, personal care products, adhesives, coatings, and the like. The
functionalized polymers may be used as base oils for lubricants and
functional fluids, and for providing functional additives for lubricants,
functional fluids and fuels. The functionalized polymers may be referred
to as polymeric resins.

[0332] The olefin comonomer may contain from 2 to about 30 carbon atoms,
or from 2 to about 24 carbon atoms, or from about 6 to about 24 carbon
atoms. The olefin comonomer may comprise an alpha olefin, an internal
olefin, or a mixture thereof. The internal olefin may be symmetric or
asymmetric. The olefin may be linear or branched. The olefin may be a
monoene, diene, triene, tetraene, or mixture of two or more thereof. The
monoenes may comprise one or more of ethene, 1-propene, 1-butene,
2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, cyclopentene,
1-hexene, 2-hexene, 3-hexene, cyclohexene, 1-heptene, 2-heptene,
3-heptene, 1-octene, 2-octene, 3-octene, 1-nonene, 2-nonene, 3-nonene,
4-nonene, 1-decene, 1-undecene, 1-dodecene; 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene,
2-methyl-2-butene, 3-methyl-1-butene, 2-methyl-1-pentene,
3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,
3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene,
2,2-dimethyl-3-pentene, styrene, vinyl cyclohexane, or a mixture of two
or more thereof. The dienes, trienes and tetraenes may comprise
butadiene, isoprene, hexadiene, decadiene, octatriene, ocimene,
farnesene, or a mixture of two or more thereof.

[0333] The olefin comonomer may be a conjugated diene. The conjugated
diene may include one or more dienes containing from 4 to about 12 carbon
atoms, or from about 4 to about 8 carbon atoms. Examples may include
1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2-ethylbutadiene,
2-propylbutadiene, 2-propyl butadiene, 2-butylbutadiene,
2-octylbutadiene, 4-methylpentadiene, 2,3-dimethylbutadiene, 2-phenyl
butadiene, 1-chlorobutadiene, 2-methoxybutadiene, or a mixture of two or
more thereof.

[0334] The acrylic acids, acrylic acid esters, methacrylic acids and
methacrylic acid esters (which collectively may be referred to as (meth)
acrylic acids and/or esters) may be represented by the following formula:

CH2═C(R1)C(O)OR2

wherein R1 is hydrogen or a methyl group, and R2 is hydrogen or
a hydrocarbyl group containing from 1 to about 30 carbon atoms, or from 1
to about 20, or from 1 to about 10 carbon atoms, and optionally, one or
more sulfur, nitrogen, phosphorus, silicon, halogen and/or oxygen atoms.
Examples may include methyl(meth)acrylate, ethyl(meth)acrylate,
propyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate,
hexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,
N,N-dimethylaminoethyl(meth)acrylate,
N,N-diethylaminoethyl(meth)acrylate, 2-sulfoethyl(meth)acrylate,
trifluoroethyl(meth)acrylate, glycidyl(meth)acrylate,
benzyl(meth)acrylate, 2-chloroethyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, phenyl(meth)acrylate, acrylamide, and
mixtures of two or more thereof.

[0335] The unsaturated nitriles may comprise acrylonitrile or
C1-C4 alkyl derivatives thereof. These may include
acrylonitrile, methacrylonitrile, and the like.

[0336] The alkenyl-substituted aromatic compounds may comprise an alkenyl
group attached to an aromatic group. The alkenyl group may contain from 2
to about 30 carbon atoms. The alkenyl group may include a carbon-carbon
double bond in alpha-position to the aromatic group. The alkenyl group
may be a vinyl group. The aromatic group may be mononuclear, such as
phenyl, or polynuclear. The polynuclear compounds or groups may be of the
fused type wherein an aromatic nucleus is fused at two points to another
nucleus such as found in anthranyl. The polynuclear group may be of the
linked type wherein at least two nuclei (either mononuclear or
polynuclear) are linked through bridging linkages to each other. The
bridging linkages may include carbon-to-carbon single bonds, ether
linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to
about 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, alkylene
linkages, alkylidene linkages, alkylene ether linkages, alkylene keto
linkages, alkylene sulfur linkages, alkylene polysulfide linkages, amino
linkages, polyamino linkages, mixtures of such divalent bridging
linkages, and the like. Examples may include styrene; ortho, meta, or
para-methylstyrene; ortho-, meta- or para-ethylstyrene;
o-methyl-p-isopropylstyrene; p-chlorostyrene; p-bromostyrene; ortho-,
meta- or para-methoxystyrene; vinylnaphthalene; and mixtures of two or
more thereof.

[0337] The vinyl ester monomers may be derived from carboxylic acids
containing 1 to about 30, or 1 to about 20, or 1 to about 10 carbon
atoms. These may include vinyl acetate, vinyl propionate, vinyl
hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl laurate, and
mixtures of two or more thereof. The vinyl ethers may include methyl-,
ethyl-, and/or butyl vinyl ethers.

[0338] The halogenated monomers, that is, fluorine, chlorine, bromine,
and/or iodine-containing monomers, may contain from 2 to about 30 carbon
atoms and at least one halogen atom. These may include vinyl halides.
Examples of these monomers may include vinyl fluoride, vinyl chloride,
vinyl bromide, vinylidene fluoride, vinylidene chloride, halogenated
(meth)acrylic acid, allyl chloride and mixtures of two or more thereof.

[0339] The unsaturated polycarboxylic acids and derivatives thereof may
include unsaturated polycarboxylic acids and their corresponding
anhydrides. These may include those which have at least one ethylenic
linkage in an alpha, beta-position with respect to at least one carboxyl
group. Exemplary acids and anhydrides may include maleic acid, maleic
anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic
acid, citraconic anhydride, mesaconic acid, mesaconic anhydride,
glutaconic acid, glutaconic anhydride, chloromaleic acid, aconitic acid,
mixtures of two or more thereof, and the like.

[0340] The polyhydric alcohols may contain from 2 to about 10 carbon
atoms, and from 2 to about 6 hydroxyl groups. Examples may include
ethylene glycol, glycerol, trimethylolpropane, 1,2-propanediol,
1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,
2-ethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl
glycol, 2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol,
mixtures of two or more thereof, and the like.

[0341] The polyamines and polyalkylene polyamines may be represented by
the formula

##STR00030##

wherein each R is independently hydrogen, a hydrocarbyl group or a
hydroxy-substituted hydrocarbyl group containing up to about 30 carbon
atoms, or up to about 10 carbon atoms, with the proviso that at least two
of the R groups are hydrogen, n is a number in the range from 1 to about
10, or from about 2 to about 8, and R1 is an alkyene group
containing 1 to about 18 carbon atoms, or 1 to about 10 carbon atoms, or
from about 2 to about 6 carbon atoms. Examples of these polyamines may
include methylene polyamine, ethylene polyamine, propylene polyamine,
butylenes polyamine, pentylene polyamine, hexylene polyamine, heptylene
polyamine, ethylene diamine, triethylene tetramine,
tris(2-aminoethyl)amine, propylene diamine, trimethylene diamine,
hexamethylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene)triamine, tripropylene tetramine, tetraethylene
pentamine, trimethylene diamine, pentaethylene hexamine,
di(trimethylene)triamine, 2-heptyl-3-(2-aminopropyl)imidazoline,
1,3-bis(2-amino-ethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine,
2-methyl-1-(2-aminobutyl)piperazine, or a mixture of two or more thereof.

[0342] The isocyanate monomers may include one or more isocyanate groups
(--N═C═O). These may include monoisocyanates and diisocyanates.
Examples may include methyl isocyanate, methylene diphenyl diisocyanate,
toluene diisocyanate, isophorone diisocyanate, and mixtures of two or
more thereof.

[0343] The alkenyl-substituted heterocyclic monomers may include
heterocyclic compounds wherein the hetero atom is N, O or S. The alkenyl
group may contain from 2 to about 30 carbon atoms. The alkenyl group may
be a vinyl group. The heterocyclic group may be a 5 or 6 member ring.
Examples may include vinyl pyridine, N-vinyl pyrolidone, mixtures
thereof, and the like.

[0344] The organosilanes may include gamma-aminopropyltrialkoxysilanes,
gamma-isocyanatopropyltriethoxysilane, vinyl-trialkoxysilanes,
glycidoxypropyltrialkoxysilanes, ureidopropyltrialkoxysilanes, and
mixtures of two or more thereof.

[0345] The olefin comonomer may comprise decene and the functionalized
monomer may comprise 9-decenoic acid or an ester derivative thereof;
10-undeceneoic acid or an ester derivative thereof, 9-octadecenedioic
acid or a mono- or di-ester derivative thereof, or a mixture of two or
more thereof.

[0346] The olefin comonomer may comprise decene, dodecene, or a mixture
thereof, and the functionalized monomer may comprise 9-decenoic acid, a
functionalized derivative of 9-decenoic acid, or a mixture thereof.

[0347] The olefin comonomer may comprise decene, dodecene, or a mixture
thereof, and the functionalized monomer may comprise a pentaerythritol
tetra-ester derivative of 9-decenoic acid.

[0348] Trans-esterification of 9-decenoic acid with pentaerythritol may
provide an ester having up to about four olefins, thereby enabling
formation of star or network-type copolymers. The tetra esters may be
used as co-monomers with traditional olefins to provide for viscosity
index improvers and post-functionalized with polyamines, polyhydric
alcohols, or alkali and alkaline-earth metal bases to provide materials
with dispersant, detergent and/or fuel economy properties.

[0349] The functionalized polymer and/or copolymer may comprise a
metathesized oligomer or polymer when the polymer is a homopolymer or
copolymer derived from one or more functionalized monomers, or a
copolymer derived from one or more functionalized monomers and one or
more comonomers.

[0350] The functionalized polymer may comprise a homopolymer wherein a
single functionalized monomer is polymerized. The functionalized polymer
may comprise a copolymer when two or more functionalized monomers are
copolymerized.

[0351] The functionalized copolymer may be derived from one or more of the
functionalized monomers and one or more comonomers wherein from about 5
to about 99 mole percent, or from about 5 to about 70 mole percent, or
from about 5 to about 50 mole percent, or from about 5 to about 30 mole
percent, of the repeating units are derived from the functionalized
monomer.

[0352] The functionalized polymer or copolymer may be reacted with one or
more enophilic reagents to form one or more polyfunctionalized polymers
or copolymers. This is described below.

[0353] The functionalized polymer and/or functionalized copolymer may have
a number average molecular weight in the range from about 300 to about
50,000, or from about 300 to about 20,000, or from about 300 to about
10,000, or from about 300 to about 5,000, or from about 500 to about
3000, as determined by gel permeation chromatography (GPC), NMR
spectroscopy, vapor phase osometry (VPO), wet analytical techniques such
as acid number, base number, saponification number or oxirane number, and
the like.

[0354] The polymer and/or copolymer may be formed using conventional
polymerization techniques. The polymerization process may comprise a
batch process, a continuous process, or a staged process. Polymerization
may be effected either via the one or more carbon-carbon double bonds,
the functional groups and/or the additional functionality provided by the
enophilic reagent. Polymerization may be effected through a condensation
reaction between one or more of the functionalized monomers,
polyfunctionalized monomers, and/or comonomers. The polymerization may
involve employing one or more cationic, free radical, anionic,
Ziegler-Natta, organometallic, metallocene, or ring-opening metathesis
polymerization (ROMP) catalysts. Free radical initiators may include azo
compounds, peroxides, light (photolysis), and combinations thereof. The
azo compounds may include azobisisobutyronitrile,
1,1'-azobis(cyclohexanecarbonitrile), and the like, and combinations
thereof. The peroxide compounds may include benzoyl peroxide, methyl
ethyl ketone peroxide, tert-butyl peroxide, di-tert-butylperoxide,
lauroyl peroxide, dicumyl peroxide, tert-butyl perpivalate, di-tert-amyl
peroxide, dicetyl peroxydicarbonate, tert-butyl peracetate,
2,2-bis(tert-butylperoxy)butane,
2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,
2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, and the like, and
combinations thereof. The free radical initiator may comprise di-t-butyl
peroxide.

[0355] Polymerization may be achieved under cationic conditions and, in
such embodiments, the acid catalyst may comprise a Lewis Acid, a Bronsted
acid, or a combination thereof. The Lewis acids may include BF3,
AlCl3, zeolite, and the like, and complexes thereof, and
combinations thereof. The Bronsted acids may include HF, HCl,
H2SO4, phosphoric acid, acid clay, Amberlyst 15,
trifluoromethanesulfonic acid (CF3SO3H), fluorosulfonic acid
(FSO3H), and the like, and combinations thereof.

[0356] Polymerization may be achieved using an olefin polymerization
catalyst (e.g., BF3) and a promoter (e.g., an alcohol) or a dual
promoter (e.g., an alcohol and an ester) as described U.S. Pat. Nos.
7,592,497 B2 and 7,544,850 B2, the teachings of which are incorporated by
reference.

[0357] The catalysts described herein may be supported on a support. For
example, the catalysts may be deposited on, contacted with, vaporized
with, bonded to, incorporated within, adsorbed or absorbed in, or on, one
or more supports or carriers. The catalysts described herein may be used
individually or as mixtures. The polymerizations using multiple catalysts
may be conducted by addition of the catalysts simultaneously or in a
sequence.

[0358] The functionalized polymer and/or copolymer may comprise a mixture
of different size polymers. Although the degree of polymerization (DP) of
a polymer and/or copolymer in accordance with the present teachings is
not restricted, it is to be understood that polymerization may result in
mixtures of polymers having different DP values. The DP of the
functionalized polymers and/or copolymers may range from about 2 to about
350. It is to be understood that some polymers in the mixture may
correspond to homopolymers of the functionalized monomers and/or
comonomers, as well as to copolymers. The functionalized polymer and/or
copolymer may have number average molecular weights in the range from
about 300 to about 50,000, or in the range from about 300 to about
25,000, or in the range from about 300 to about 10,000 or in the range
from about 500 and about 3000, as determined by gel permeation
chromatography (GPC), spectroscopy, vapor phase osometry (VPO), wet
analytical techniques such as acid number, base number, saponification
number or oxirane number, and the like.

[0359] In an embodiment, the functionalized polymer and/or copolymer may
be represented by the following structure:

##STR00031##

wherein: R, R1, and R2 may be independently hydrogen, a
C1-C22 alkyl, or --CH2(CH2)oCH2X. When
R1 and R2 are alkyl groups, the total number of carbon atoms in
these groups may be in the range from about 4 to about 35 carbon atoms. X
may be --OH, --NH2, alkylamino, dialkylamino, or --CO2R3,
wherein R3 may be hydrogen or a C1-C10 alkyl group derived
from a monohydric alcohol, polyhydric alcohol, amine, and/or polyalkylene
polyamine. m may be an integer from 0 to about 400. n may be an integer
from 1 to about 300. m+n may be in the range from 1 to about 320. o may
be an integer from 1 to about 16. z may be an integer from 1 to about
350.

[0360] The functionalized polymer or copolymer may be combined with other
polymers by methods known to those skilled in the art. These may include
polyurethanes, polyacrylates, polyesters, silicones, and the like.

[0361] Adjuvants useful in the preparation of the functionalized polymer
or copolymer and/or in their subsequent use may be added during or
subsequent to the polymerization reaction. These may include defoamers,
leveling agents, antioxidants, thixotropic additives, plasticizers,
preservatives, and mixtures of two or more thereof.

[0362] The functionalized polymer or copolymers, or polyfunctionalized
polymers or copolymers may be suitable for use in polymeric or plastic
formulations for making extruded or molded articles, or for use in
adhesives, coating compositions, including protective and/or decorative
coatings (e.g., paint), or for use in pharmaceuticals, cosmetics,
personal care products, and the like.

Reaction of the Functionalized Monomers and Polymers with Enophilic
Reagents

[0363] The functionalized monomers and/or polymers or copolymers may be
reacted with an enophilic reagent to form polyfunctionalized monomers,
polymers and/or copolymers. This may provide the functionalized monomers
and polymers with additional levels of functionality. The enophilic
reagent may comprise an enophilic acid reagent, an oxidizing agent, an
aromatic compound, a sulfurizing agent, a sulfonating agent,
hydroxylating agent, halogenating agent, or a mixture of two or more
thereof. The enophilic reagent may be reactive towards one or more of the
carbon-carbon double bonds in the functionalized monomer or polymer. The
polyfunctionalized monomer may be polymerized to form a
polyfunctionalized polymer. Similarly, the polyfunctionalized monomer may
be copolymerized with a comonomer to form a polyfunctionalized copolymer.

[0365] The polymerization procedure may be the same as discussed above, or
it may comprise an acid- or base-catalyzed condensation type
polymerization. The polyfunctionalized polymer and/or polyfunctionalized
copolymer may have a number average molecular weight in the range from
about 300 to about 50,000, or from about 300 to about 20,000, or from
about 300 to about 10,000, or from about 300 to about 5,000, or from
about 500 to about 3000, as determined by gel permeation chromatography
(GPC), NMR spectroscopy, vapor phase osmometry (VPO), wet analytical
techniques such as acid number, base number, saponification number or
oxirane number, and the like.

[0366] The ratio of the reactants in the reaction between the
functionalized monomer or polymer and the enophilic reagent may be
measured by the ratio of the reaction equivalents of the monomer or
polymer in the reaction to the reaction equivalents of the enophilic
reagent in the reaction. The number of equivalents of the functionalized
monomer or polymer may be based on the number of carbon-carbon double
bonds in the monomer or polymer. Thus, for example, one mole of a
functionalized monomer having two carbon-carbon double bonds in its
hydrocarbyl group would have an equivalent weight equal to one-half a
mole of the monomer, if the reaction of both double bonds is intended.
However, if the reaction of one double bond is intended, then the
equivalent weight of such a compound will be the same as its molecular
weight. The number average molecular weight of an equivalent of a
functionalized polymer having an overall number average molecular weight
of 1000 and five carbon-carbon double bonds in its molecular structure
would be 200, 400, 600, 800, and 1000; depending upon the number of
double bonds taking part in the reaction.

Enophilic Acid-Functionalized Derivative

[0367] The functionalized monomer or functionalized polymer of the
invention may be reacted with an enophilic acid reagent to form an
enophilic acid functionalized derivative. This derivative may be referred
to as a polyfunctionalized monomer or polymer.

[0368] The enophilic acid reagent may comprise one or more alpha-beta
olefinically unsaturated carboxylic acids and/or derivatives thereof. The
derivative may comprise one or more olefinic acids, anhydrides, esters,
amides, aldehydes, and/or acyl halides. The carboxylic acid or derivative
may comprise one or more monobasic and/or polybasic alpha-beta
olefinically unsaturated carboxylic acids or derivatives thereof. The
monobasic carboxylic acids may comprise one or more compounds represented
by the formula

##STR00032##

wherein R1 and R2 are independently hydrogen or hydrocarbyl
groups. R1 and R2 independently may be hydrocarbyl groups
containing 1 to about 20 carbon atoms, or from 1 to about 12 carbon
atoms, or from 1 to about 4 carbon atoms.

[0369] The polybasic carboxylic acid reagents may comprise one or more
alpha, beta unsaturated dicarboxylic acids or derivatives thereof. These
may include those wherein a carbon-carbon double bond is in an alpha,
beta-position to at least one of the carboxy functions (e.g., itaconic
acid, or derivative thereof) or in an alpha, beta-position to both of the
carboxy functions (e.g., maleic acid, anhydride or derivative thereof).
The carboxy functions of these compounds may be separated by up to about
4 carbon atoms, or about 2 carbon atoms.

[0371] The ratio of equivalents of the functionalized monomer or
functionalized polymer to equivalents the enophilic acid reagent may be
from about 1 to about 4, or from about 1 to about 2. The weight of an
equivalent of an enophilic acid reagent is dependent on the number of
carbon-carbon double bonds and/or reactive functional groups in its
molecular structure. For example, one mole of an enophilic acid reagent
having one carbon-carbon double bond in its molecular structure (e.g.,
maleic anhydride) would have an equivalent weight equal to its molecular
weight, if the reaction was with an olefin, commonly referred to as ene
reaction. However, if maleic anhydride or its ene reaction product, an
alkenylsuccinic anhydride, were used in an esterification reaction, their
equivalent weights would be one-half those of their molecular weights. If
the ene product, which would have a single carbon-carbon double bond,
underwent another ene reaction, its equivalent weight would be the same
as its molecular weight.

[0372] The reaction between the functionalized monomer or functionalized
polymer and the enophilic acid reagent may be carried out in the presence
of a catalyst. The catalyst may comprise a dialkylperoxide, or a Lewis
acid such as AlCl3.

[0373] The reaction of the functionalized monomer or functionalized
polymer with the enophilic acid reagent may be enhanced by heating the
reaction mixture (with or without a catalyst) to a temperature in the
range from about 100° C. to about 300° C., or from about
150° C. to about 250° C.

[0374] The amount of catalyst added to the reaction may be from about 5
percent by weight to about 15 percent by weight of the functionalized
monomer or functionalized polymer, or from about 5 percent by weight to
about 10 percent by weight.

[0375] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere. The time of reaction may range from about 1 to
about 24 hours, or from about 6 to about 12 hours.

[0376] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Oxidized Derivative

[0377] The functionalized monomer or functionalized polymer of the
invention may be reacted with one or more oxidizing agents. This may
result in the formation of one or more oxidized derivatives which may be
in the form of one or more epoxides. These may be referred to as
polyfunctionalized monomers or polymers

[0378] The oxidizing agent may comprise any compound that provides oxygen
atoms for reaction with one or more of the carbon-carbon double bonds of
the functionalized monomer or functionalized polymer. The oxidizing agent
may comprise any compound containing an oxygen-oxygen single bond, or a
peroxide group or peroxide ion. Examples include hydrogen peroxide,
organic peroxides such as peroxy acids (e.g., peroxy carboxylic acid) and
organic hydroperoxides (e.g., cumene hydroperoxide), and inorganic
peroxides such as peroxide salts (e.g., alkali metal or alkaline earth
metal peroxides) and acid peroxides (e.g., peroxymonosulfuric acid,
peroxydisulfuric acid, and the like).

[0379] The ratio of equivalents of the functionalized monomer or
functionalized polymer to equivalents of the oxidizing agent may be from
about 3 to about 1, or from about 2 to about 1. The weight of an
equivalent of an oxidizing agent is dependent on the number of oxygen
atoms in the oxidizing agent that are reactive with the carbon-carbon
double bonds in the functionalized monomer or polymer. For example, one
mole of an oxidizing agent having one oxygen atom available for reaction
with the carbon-carbon double bonds in the functionalized monomer or
polymer would have an equivalent weight equal to a fraction of the
molecular weight of the oxidizing agent, depending upon the number of
carbon-carbon double bonds in the molecule being oxidized.

[0380] The reaction between the functionalized monomer or functionalized
polymer and the oxidizing agent may be carried out in the presence of a
catalyst. The catalyst may comprise Amberlyst (polymer based catalyst
available from Rohm & Haas), Amberlite (ion exchange resin available from
Rohm & Haas), formic acid, acetic acid and/or sulfuric acid.

[0381] The reaction of the functionalized monomer or functionalized
polymer with the oxidizing agent may be enhanced by heating the reaction
mixture (with or without a catalyst) to a temperature in the range from
about 30° C. to about 180° C., or from about 50° C.
to about 70° C.

[0382] The amount of catalyst added to the reaction may be from about 5
percent by weight to about 25 percent by weight of the functionalized
monomer or functionalized polymer in the reaction mixture, or from about
5 percent by weight to about 20 percent by weight.

[0383] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere, in a solvent or neat (without solvent). The time
of reaction may range from about 6 to about 24 hours, or from about 8 to
about 12 hours.

[0384] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Alkylated Aromatic Compound

[0385] The functionalized monomer or functionalized polymer of the
invention may be reacted with one or more aromatic compounds to form an
alkylated aromatic compound. These may be referred to as alkylation
reactions wherein the functionalized monomer or polymer may be attached
to the aromatic compound via one or more of the carbon-carbon double
bonds in the functionalized monomer or polymer. The product may be
referred to as a polyfunctionalized monomer or polymer.

[0386] The aromatic compound may comprise any aromatic compound capable of
reacting with the functionalized monomer or polymer of the invention. The
aromatic compound may comprise an aromatic, aliphatic-substituted
aromatic, or aromatic-substituted aliphatic compound. The aromatic
compound may comprise a substituted aromatic compound, that is, an
aromatic compound containing one or more non-hydrocarbon groups such as
hydroxyl, halo, nitro, amino, cyano, alkoxy, acyl, epoxy, acryloxy,
mercapto, mixtures of two or more thereof, and the like. The aromatic
compound may comprise a hetero substituted aromatic compound, that is, an
aromatic compound containing one or more atoms other than carbon in a
chain or ring otherwise comprising carbon atoms; examples of such hetero
atoms including nitrogen, oxygen and sulfur.

[0387] The aromatic compound may comprise one or more of benzene,
naphthalene, naphthacene, alkylated derivatives thereof, and the like.
The aromatic compound may contain from 6 to about 40 carbon atoms, or
from 6 to about 30 carbon atoms, or from 6 to about 20 carbon atoms, or
from 6 to about 15 carbon atoms, or from 6 to about 12 carbon atoms.
Examples may include benzene, toluene, ethylbenzene, styrene,
alpha-methyl styrene, propylbenzene, xylene, mesitylene,
methylethylbenzene, naphthalene, anthracene, phenanthrene,
methynaphthalene, dimethylnaphthalene, tetralin, mixtures of two or more
thereof, and the like. The aromatic compound may comprise phenol and/or
its derivatives, dihydroxybenzene, naphthol and/or dihydroxynaphthalene.
The aromatic compound may comprise an aromatic amine and/or a pyridine.
The aromatic compound may comprise aniline, diphenylamine, toluidine,
phenylenediamine, diphenylamine, alkyldiphenylamine, and/or
phenothiazine. The aromatic compound may comprise an alkylbenzene with a
multi-substituted benzene ring, examples including o-, m- and p-xylene,
toluene, tolyl aldehyde, toluidine, o-, m- and p-cresol, phenyl aldehyde,
mixtures of two or more thereof, and the like.

[0388] The ratio of equivalents of the functionalized monomer or polymer
to equivalents of the aromatic compound may be from about 4:1 to about
1:1, or from about 2:1 to about 1:1. The weight of an equivalent of an
aromatic compound would be equal to the molecular weight of the aromatic
compound, if only a single carbon-carbon double bond were to take part in
the reaction. Otherwise, it would be a fraction of 1 (i.e., less than 1).

[0389] The reaction between the functionalized monomer or polymer and the
aromatic compound may be carried out in the presence of a catalyst. The
catalyst may comprise a Lewis acid, Bronsted acid, acid clay and/or
zeolite.

[0390] The reaction of the functionalized monomer or polymer with the
aromatic compound may be enhanced by heating the reaction mixture (with
or without a catalyst) to a temperature in the range from about
50° C. to about 300° C., or from about 100° C. to
about 200° C.

[0391] The amount of catalyst added to the reaction may be from about 1
percent by weight to about 100 percent by weight of the functionalized
monomer or polymer in the reaction mixture, or from about 30 percent by
weight to about 50 percent by weight.

[0392] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere. The time of reaction may range from about 2 to
about 24 hours, or from about 6 to about 12 hours.

[0393] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Sulfurized Derivative

[0394] The functionalized monomer or polymer of the invention may be
reacted with one or more sulfurizing agents to form a sulfurized
derivative. The sulfurized derivative may be referred to as a
polyfunctionalized monomer or polymer.

[0395] The sulfurizing agent may comprise elemental sulfur and/or any
suitable sulfur source. The sulfur source may comprise a variety of
materials capable of supplying sulfur to the reaction. Examples of useful
sulfur sources may include sulfur halides, combinations of sulfur or
sulfur oxides with hydrogen sulfide, and various sulfurized organic
compounds as described below. The sulfur halides may include sulfur
monochloride, sulfur dichloride, mixtures thereof, and the like.
Combinations of sulfur and sulfur oxides (such as sulfur dioxide), with
hydrogen sulfide may be used.

[0396] The sulfurizing agent may comprise one or more of the
sulfur-coupled compounds. These may include one or more sulfur-coupled
organic compounds, for example, disulfides (RSSR), trisulfides
(RS3R), polysulfides (RSxR, where x is from 4 to 7), mixtures
of two or more thereof, and the like.

[0397] The sulfurizing agent may comprise one or more phosphorus sulfides.
Examples may include P2S5, P4S10, P4S7,
P4S3 and P2S3, mixtures of two or more thereof, and
the like.

[0398] The sulfurizing agent may comprise one or more aromatic and/or
alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl
sulfide, diparaffin wax sulfide and/or polysulfide, cracked wax oleum
sulfides, mixtures of two or more thereof, and the like. The aromatic and
alkyl sulfides may be prepared by the condensation of a chlorinated
hydrocarbon with an inorganic sulfide whereby the chlorine atom from each
of two molecules may be displaced, and the free valence from each
molecule may be joined to a divalent sulfur atom. The reaction may be
conducted in the presence of elemental sulfur.

[0399] Dialkenyl sulfides that may be used may be prepared by reacting an
olefinic hydrocarbon containing from about 3 to about 12 carbon atoms
with elemental sulfur in the presence of zinc or a similar metal
generally in the form of an acid salt. Examples of sulfides of this type
may include 6,6'-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfide and
disulfide, and 2-methyl-2-butenyl monosulfide and disulfide.

[0400] Sulfurized olefins which may be used as the sulfurizing agent may
include sulfurized olefins prepared by the reaction of an olefin of about
3 to about 6 carbon atoms, or a lower molecular weight polyolefin derived
therefrom, with a sulfur-containing compound such as sulfur, sulfur
monochloride, sulfur dichloride, hydrogen sulfide, mixtures of two or
more thereof, and the like.

[0401] The sulfurizing agent may comprise one or more sulfurized oils
which may be derived from one or more natural or synthetic oils including
mineral oils, lard oil, carboxylic acid esters derived from aliphatic
alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl
oleate and oleyl oleate), sperm whale oil and synthetic sperm whale oil
substitutes, and synthetic unsaturated esters or glycerides. Sulfurized
mineral oils may be obtained by heating a suitable mineral oil with from
about 1 to about 5% by weight of sulfur at a temperature in the range
from about 175° C. to about 260° C. The mineral oils
sulfurized in this manner may be distillate or residual oils obtained
from paraffinic, naphthenic or mixed base crudes. Sulfurized fatty oils
such as a sulfurized lard oil may be obtained by heating lard oil with
about 10 to 15% of sulfur at a temperature of about 150° C. for a
time sufficient to obtain a homogeneous product.

[0403] Another class of organic sulfur-containing compounds which may be
used as the sulfurizing agent may include sulfurized aliphatic esters of
olefinic mono- or dicarboxylic acids. For example, aliphatic alcohols of
from 1 to about 30 carbon atoms may be used to esterify monocarboxylic
acids such as acrylic acid, methacrylic acid, 2,4-pentadienic acid,
fumaric acid, maleic acid, muconic acid, etc. Sulfurization of these
esters may be conducted with elemental sulfur, sulfur monochloride and/or
sulfur dichloride.

[0404] Another class of sulfurized organic compounds which may be used as
the sulfurizing agent may include diestersulfides represented by the
formula

Sy((CH2)xCOOR)2

wherein x is a number in the range of about 2 to about 5; y is a number
in the range of 1 to about 6, or 1 to about 3; and R is an alkyl group
having from about 4 to about 20 carbon atoms. The R group may be a
straight chain or branched chain group. Typical diesters may include the
butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, myristyl,
pentadecyl, cetyl, heptadecyl, stearyl, lauryl, and eicosyl diesters of
thiodialkanoic acids such as propionic, butanoic, pentanoic and hexanoic
acids. The diester sulfides may include dilauryl 3,3'-thiodipropionate.

[0405] The sulfurizing agent may comprise one or more sulfurized olefins.
These may include the organic polysulfides which may be prepared by the
sulfochlorination of olefins containing four or more carbon atoms and
further treatment with inorganic higher polysulfides according to U.S.
Pat. No. 2,708,199, the teachings of which are incorporated by reference.

[0406] The sulfurized olefins may be produced by (1) reacting sulfur
monochloride with a stoichiometric excess of a low carbon atom olefin,
(2) treating the resulting product with an alkali metal sulfide in the
presence of free sulfur in a mole ratio of no less than 2:1 in an
alcohol-water solvent, and (3) reacting that product with an inorganic
base. This procedure is described in U.S. Pat. No. 3,471,404, the
teachings of which are incorporated by reference. The olefin reactant may
contain from about 2 to about 5 carbon atoms. Examples may include
ethylene, propylene, butylene, isobutylene, amylene, and mixtures of two
or more thereof. In the first step, sulfur monochloride may be reacted
with from one to two moles of the olefin per mole of the sulfur
monochloride. The reaction may be conducted by mixing the reactants at a
temperature of from about 20° C. to 80° C. In the second
step, the product of the first step may be reacted with an alkali metal,
preferably sodium sulfide, and sulfur. The mixture may comprise up to
about 2.2 moles of the metal sulfide per gram atom of sulfur, and the
mole ratio of alkali metal sulfide to the product of the first step may
be about 0.8 to about 1.2 moles of metal sulfide per mole of step (1)
product. The second step may be conducted in the presence of an alcohol
or an alcohol-water solvent under reflux conditions. The third step of
the process may comprise the reaction between the phosphosulfurized
olefin which may contain from about 1 to about 3% of chlorine with an
inorganic base in a water solution. Alkali metal hydroxide such as sodium
hydroxide may be used. The reaction may be continued until the chlorine
content is reduced to below about 0.5%. This reaction may be conducted
under reflux conditions for a period of from about 1 to about 24 hours.

[0407] The sulfurizing agent may be prepared by the reaction, under
superatmospheric pressure, of olefinic compounds with a mixture of sulfur
and hydrogen sulfide in the presence of a catalyst, followed by removal
of low boiling materials. This procedure is described in U.S. Pat. No.
4,191,659, the teachings of which are incorporated by reference. An
optional final step described in this patent is the removal of active
sulfur by, for example, treatment with an alkali metal sulfide. The
olefinic compounds which may be sulfurized by this method may contain at
least one carbon-carbon double bond. These compounds may be represented
by the formula

R1R2C═CR3R4

wherein each of R1, R2, R3 and R4 is hydrogen or a
hydrocarbyl group. Any two of R1, R2, R3 and R4 may
together form an alkylene or substituted alkylene group; i.e., the
olefinic compound may be alicyclic.

[0408] The ratio of equivalents of the functionalized monomer or polymer
to equivalents of the sulfurizing agent may be from about 1 to about 10,
or from about 1 to about 6. The weight of an equivalent of a sulfurizing
agent is dependent on the number of sulfur atoms in the sulfurizing agent
that are reactive with the carbon-carbon double bonds in the
functionalized monomer or polymer. For example, one mole of a sulfurizing
agent having one sulfur atom available for reaction with the
carbon-carbon double bonds in the functionalized monomer or polymer would
have an equivalent weight equal to the molecular weight of the
sulfurizing agent.

[0409] The reaction between the functionalized monomer or polymer and the
sulfurizing agent may be carried out in the presence of a catalyst. The
catalyst may comprise tertiary phosphine, iodine, BF3, metal
dithiocarbamate, and the like.

[0410] The reaction of the functionalized monomer or polymer with the
sulfurizing agent may be enhanced by heating the reaction mixture (with
or without a catalyst) to a temperature in the range from about
130° C. to about 200° C., or from about 150° C. to
about 180° C.

[0411] The amount of catalyst added to the reaction may be from about 1
percent by weight to about 20 percent by weight of the functionalized
monomer or polymer, or from about 5 percent by weight to about 10 percent
by weight.

[0412] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere. The time of reaction may range from about 2 to
about 8 hours, or from about 4 to about 6 hours.

[0413] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Sulfonated Derivative

[0414] The functionalized monomer or polymer of the invention may be
reacted with one or more sulfonating agents to form a sulfonated
derivative. The sulfonated derivative may be referred to as a
polyfunctionalized monomer or polymer.

[0415] The sulfonating agent may comprise any compound that provides a
sulfonate group for reaction with one or more of the carbon-carbon double
bonds of the olefin. The sulfonating agent may comprise sulfur trioxide,
oleum, chlorosulfonic acid, sodium bisulfite, or a mixture of two or more
thereof.

[0416] The ratio of equivalents of the functionalized monomer or polymer
to equivalents of the sulfonating agent may be from about 1 to about 2,
or from about 1 to about 1. The weight of an equivalent of a sulfonating
agent is dependent on the number of sulfonate groups in the sulfonating
agent that are reactive with the carbon-carbon double bonds in the
functionalized monomer or polymer. Since most sulfonating agents have
only one sulfonating group, their equivalent weight is the same as their
molecular weight. However, the equivalent weight of the functionalized
monomer or polymer will depend upon the number of carbon-carbon double
bond intended to be sulfonated. If it were one, then their equivalent
weight would be the same as their molecular weight. If there were more
than one carbon-carbon double bond to be sulfonated, then the equivalent
weight would be a fraction of the molecular weight.

[0417] The reaction between the functionalized monomer or polymer and the
sulfonating agent may be carried out in the presence of a catalyst. The
catalyst may comprise a hydroperoxide, oxygen, and the like.

[0418] The reaction of the functionalized monomer or polymer with the
sulfonating agent may be enhanced by heating the reaction mixture (with
or without a catalyst or a solvent) to a temperature in the range from
about -30° C. to about 50° C., or from about -5° C.
to about 25° C.

[0419] The amount of catalyst added to the reaction may be from about 1
percent by weight to about 10 percent by weight of the functionalized
monomer or polymer in the reaction mixture, or from about 2 percent by
weight to about 5 percent by weight. The time of reaction may range from
about 1 to about 5 hours, or from about 2 to about 3 hours.

[0420] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Hydroxylated Derivative

[0421] The functionalized monomer or polymer of the invention may be
reacted with one or more hydroxylating agents to form a hydroxylated
derivative. The hydroxylated derivative may be referred to as a
polyfunctionalized monomer or polymer.

[0422] The hydroxylation agent may comprise any compound that introduces a
hydroxyl into the monomer or polymer. The hydroxylating agent may
comprise water, hydrogen peroxide, or a mixture thereof.

[0423] The ratio of equivalents of the functionalized monomer or polymer
to equivalents of the hydroxylating agent may be from about 1 to about 8,
or from about 1 to about 4. The weight of an equivalent of an
hydroxylating agent is dependent on the number of hydroxyl groups in the
hydroxylating agent that are reactive with the carbon-carbon double bonds
in the functionalized monomer or polymer. For example, one mole of an
hydroxylating agent having one hydroxyl group available for reaction with
each carbon-carbon double bond in the functionalized monomer or polymer
would have an equivalent weight equal to the molecular weight of the
hydroxylating agent.

[0424] The reaction between the functionalized monomer or polymer and the
hydroxylating agent may be carried out in the presence of a catalyst. The
catalyst may comprise oxygen, or a strong mineral acid such as
hydrochloric acid, sulfuric acid, hydroiodic acid, or a mixture of two or
more thereof.

[0425] The reaction of the functionalized monomer or polymer with the
hydroxylating agent may be enhanced by heating the reaction mixture (with
or without a catalyst) to a temperature in the range from about
20° C. to about 100° C., or from about 25° C. to
about 60° C.

[0426] The amount of catalyst added to the reaction may be from about 1
percent by weight to about 20 percent by weight of the functionalized
monomer or polymer in the reaction mixture, or from about 5 percent by
weight to about 10 percent by weight. The time of reaction may range from
about 2 to about 12 hours, or from about 3 to about 5 hours.

[0427] Following the reaction, the product mixture may be subjected to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Halogenated Derivative

[0428] The functionalized monomer or polymer of the invention may be
reacted with one or more halogenating agents to form a halogenated
derivative. The halogenated derivative may be referred to as a
polyfunctionalized monomer or polymer.

[0429] The halogenating agent may comprise any compound that provides for
the addition of a halogen atom (e.g., F, Cl, Br, I, or a mixture of two
or more thereof) to the monomer or polymer. The halogenating agent may
comprise fluorine, chlorine, bromine, iodine, hydrogen chloride, hydrogen
bromide, hydrogen fluoride, iodine monochloride, antimony pentafluoride,
molybdenum pentachloride, nitrogen fluoride oxide, antimony
pentachloride, tungsten hexafluoride, tellurium hexafluoride, sulfur
tetrafluoride, sulfur monochloride, silicon tetrafluoride, phosphorus
pentafluoride, or a mixture of two or more thereof.

[0430] The ratio of equivalents of the functionalized monomer or polymer
to equivalents of the halogenating agent may be from about 1 to about 8,
or from about 1 to about 4. The weight of an equivalent of a halogenating
agent is dependent on the number of halogen atoms in the halogenating
agent that are reactive with each carbon-carbon double bond in the
functionalized monomer or polymer. For example, one mole of a
halogenating agent having one halogen atom available for reaction with
the carbon-carbon double bonds in the functionalized monomer or polymer
would have an equivalent weight equal to the molecular weight of the
halogenating agent.

[0431] The reaction between the functionalized monomer or polymer and the
halogenating agent may be carried out in the presence of a catalyst. The
catalyst may comprise light, oxygen, one or more peroxides, one or more
metal halides, or a mixture of two or more thereof.

[0432] The reaction of the functionalized monomer or polymer with the
halogenating agent may be enhanced by heating the reaction mixture (with
or without a catalyst) to a temperature in the range from about
20° C. to about 100° C., or from about 40° C. to
about 60° C.

[0433] The amount of catalyst added to the reaction may be from about 2
percent by weight to about 10 percent by weight of the functionalized
monomer or polymer in the reaction mixture, or from about 3 percent by
weight to about 5 percent by weight. The time of reaction may range from
about 1 to about 12 hours, or from about 2 to about 6 hours.

[0434] Following the reaction, the product mixture may be subject to
isolation of the crude material. The crude material may be subjected to a
vacuum to separate undesired volatile materials from the product.

Dispersants

[0435] The functionalized or polyfunctionalized monomer, polymer or
copolymer of the invention, optionally in combination with an
alkenylsuccinic acid and/or anhydride (e.g., polyisobutenylsuccinic
anhydride), may be reacted with a nitrogen-containing reagent and/or an
oxygen-containing reagent to form a dispersant which may be used in a
lubricant, functional fluid or fuel composition. The dispersant may
comprise the reaction product of a nitrogen-containing reagent or an
oxygen-containing reagent, with: (i) a functionalized monomer comprising
a hydrocarbyl group with one or more carbon-carbon double bonds and one
or more functional groups attached to the hydrocarbyl group, the
hydrocarbyl group containing from about 5 to about 30 carbon atoms, or
from about 6 to about 30 carbon atoms, or from about 8 to about 30 carbon
atoms, or from about 10 to about 30 carbon atoms, or from about 12 to
about 30 carbon atoms, or from about 14 to about 30 carbon atoms, or from
about 16 to about 30 carbon atoms, or from about 5 to about 18 carbon
atoms, or from about 5 to about 18 carbon atoms, or about 18 carbon
atoms, the functional group comprising a carboxylic acid group or
derivative thereof; (ii) a polymer derived from one or more of the
functionalized monomers (i); (iii) a copolymer derived from one or more
of the functionalized monomers (i) and one or more olefin comonomers;
(iv) the reaction product of an enophilic acid reagent with the monomer
(i), polymer (ii) and/or copolymer (iii); or (v) a mixture of two or more
of (i), (ii), (iii) and (iv). The olefin comonomer may contain from 2 to
about 30 carbon atoms, or from about 6 to about 24 carbon atoms. The
enophilic acid reagent may comprise one or more alpha-beta unsaturated
carboxylic acids and/or derivatives thereof.

[0436] The polymer may comprise a homopolymer derived from the
functionalized monomer or a copolymer derived from one or more of the
functionalized monomers and/or an olefin comonomer. The polymer or
copolymer may contain at least about 30 mole percent of repeating units
derived from one or more of the functionalized monomers, or at least
about 50 mole percent, or at least about 70 mole percent, or from about
30 to about 100 mole percent, or from about 50 to about 100 percent, or
from about 70 to about 100 mole percent. The olefin comonomer may contain
from 2 to about 30 carbon atoms, or from about 6 to about 24 carbon
atoms. The polymer or copolymer may have a number average molecular
weight in the range from about 2000 to about 10,000, or from about 3000
to about 6000, as determined by GPC. The polymer or copolymer may be
prepared using the procedures described above.

[0437] The functionalized monomer (i), polymer (ii), copolymer (iii)
and/or reaction product (iv) optionally may be mixed with an
alkenylsuccinic acid or anhydride such as polyisobutenylsuccinic
anhydride. The polyisobutenylsuccinic anhydride may have a number average
molecular weight in the range from about 750 to about 3000. In a mixture,
the ratio of equivalents of the functionalized monomer, polymer and/or
reaction product to equivalents of the alkenylsuccinic acid or anhydride
(e.g., polyisobutenylsuccinic anhydride) may be in the range from about 1
to about 4, or from about 1 to about 2. The weight of an equivalent of an
alkenylsuccinic acid or anhydride is dependent on the number of carbonyl
groups to be reacted with an amine or an alcohol reagent. For example,
one mole of an alkenylsuccinic acid or anhydride has two carbonyl groups
in its molecular structure, so if one of the carbonyl groups were reacted
with an amine to form a cyclic imide, the alkenylsuccinic acid or
anhydride would have an equivalent weight equal to its molecular weight.
Conversely, if both carbonyl groups were to be reacted with an amine to
form a diamide or a monohydric alcohol to form a diester, the equivalent
weight of the alkenylsuccinic acid or anhydride would be one-half of its
molecular weight.

[0438] The nitrogen-containing reagent may comprise ammonia and/or a
compound containing one or more primary and/or secondary amino groups.
These may be referred to as amines. The amine may be a monoamine or a
polyamine. The amine may be a mono-substituted amine having one
non-hydrogen substituted group (such as an alkyl, aryl group, alkyl-amino
group, or aryl-amino group), a di-substituted amine having two
non-hydrogen substituted groups, an amino-alcohol, or a combination of
two or more thereof.

[0440] The amine may be a diamine. Examples may include ethylenediamine
(1,2-ethanediamine), 1,3-propanediamine, 1,4-butanediamine (putrescine),
1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine,
1,8-octanediamine, 1,3-bis(aminomethyl)cyclohexane, meta-xylenediamine,
1,8-naphthalenediamine, p-phenylenediamine,
N-(2-aminoethyl)-1,3-propanediamine, or a mixture of two or more thereof.

[0441] The amine may be a triamine, a tetramine, or a mixture thereof.
Examples of these may include diethylenetriamine, dipropylenetriamine,
dibutylenetriamine, dipentylenetriamine, dihexylenetriamine,
diheptylenetriamine, dioctylenetriamine, spermidine, melamine,
triethylenetetramine, tripropylenetetramine, tributylenetetramine,
tripentylenetetramine, trihexylenetetramine, triheptylenetetramine,
trioctylenetetramine, hexamine, or a mixture of two or more thereof. The
amine may be an imidazole, such as aminopropylimidazole, or an
oxazolidine.

[0442] The amine may comprise ethanolamine, diethanolamine, diethylamine,
ethylenediamine, hexamethyleneamine, or a mixture of two or more thereof.
The amine may be ethylenediamine. The amine may be diethanolamine.

[0443] The amine may comprise an amino-alcohol. Examples may include
methanolamine, dimethanolamine, ethanolamine, diethanolamine,
propanolamine, dipropanolamine, butanolamine, dibutanolamine,
pentanolamine, dipentanolamine, hexanolamine, dihexanolamine,
heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline, or
a mixture of two or more thereof.

[0444] The amine may comprise a polyamine or polyalkylene polyamine
represented by the formula

##STR00033##

wherein each R is independently hydrogen, a hydrocarbyl group or a
hydroxy-substituted hydrocarbyl group containing up to about 30 carbon
atoms, or up to about 10 carbon atoms, with the proviso that at least one
R is hydrogen, n is a number in the range from 1 to about 10, or from
about 2 to about 8, and R1 is an alkyene group containing 1 to about
18 carbon atoms, or 1 to about 10 carbon atoms, or from about 2 to about
6 carbon atoms. Examples of these polyamines may include methylene
polyamine, ethylene polyamine, propylene polyamine, butylenes polyamine,
pentylene polyamine, hexylene polyamine, heptylene polyamine, ethylene
diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene
diamine, trimethylene diamine, hexamethylene diamine, decamethylene
diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene
tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene
hexamine, di(trimethylene)triamine,
2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-amino-ethyl)piperazine,
1,4-bis(2-aminoethyl)piperazine, 2-methyl-1-(2-aminobutyl)piperazine, or
a mixture of two or more thereof.

[0445] The equivalent ratio of C═O in the functionalized monomer,
polymer or copolymer, or mixture of functionalized monomer, polymer or
copolymer and alkenyl succinic acid or anhydride, to N in the amine may
be from about 1 to about 10, or from about 1 to about 5.

[0446] The reaction between the functionalized monomer, polymer or
copolymer, or mixture of functionalized monomer, polymer and/or copolymer
and alkenyl succinic acid or anhydride (e.g., polyisobutenylsuccinic
anhydride), and the amine may be carried out in the presence of a
catalyst. The catalyst, which may be a basic catalyst, may be used to
improve the reaction rate of the functionalized polymer with the amine.
The catalyst may comprise one or more of sodium carbonate, lithium
carbonate, sodium methanolate, potassium hydroxide, sodium hydride,
potassium butoxide, potassium carbonate, or a mixture thereof. The
catalyst may be added to the reaction mixture in dry form or in the form
of a solution. The reaction may be enhanced by heating the reaction
mixture (with or without a catalyst) to at least about 80° C., or
at least 100° C., or at least about 120° C., or at least
about 140° C., or at least about 160° C.

[0447] The amount of catalyst added to the reaction may be in the range
from about 0.01 percent by weight to about 5 percent by weight of the
functionalized monomer, polymer or copolymer, or mixture of
functionalized monomer, polymer or copolymer and alkenylsuccinic acid or
anhydride, in the reaction mixture, or from about 0.01 percent by weight
to about 1 percent by weight, or from about 0.2 percent by weight to
about 0.7 percent by weight.

[0448] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere. The time of reaction may range from about 1 to
about 24 hours, or from about 1 to about 12 hours, or from about 1 to
about 6 hours, or from about 1 to about 4 hours.

[0449] The oxygen-containing reagent may comprise one or more alcohols
and/or one or more polyols. The alcohols may contain from 1 to about 18
carbon atoms, or from 1 to about 8 carbon atoms. These may include
methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol,
isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, amyl
alcohol, tert-pentanol, cyclopentanol, cyclohexanol, allyl alcohol,
crotyl alcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethyl
alcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol,
cinnamyl alcohol, mixtures of two or more thereof, and the like.

[0450] The polyols may contain from 2 to about 10 carbon atoms, and from 2
to about 6 hydroxyl groups. Examples may include ethylene glycol,
glycerol, trimethylolpropane, 1,2-propanediol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,
2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,
2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures of
two or more thereof, and the like.

[0451] The equivalent ratio of C═O in the functionalized monomer,
polymer or copolymer, or mixture of functionalized monomer, polymer or
copolymer and alkenylsuccinic acid or anhydride, to --OH in the
oxygen-containing reagent may be from about 1 to about 6, or about 1.

[0452] The reaction between the functionalized monomer, polymer or
copolymer, or mixture of functionalized monomer, polymer or copolymer and
alkenylsuccinic acid or anhydride, and the oxygen-containing reagent may
be carried out in the presence of a catalyst. The catalyst may be a Lewis
acid, a Bronsted acid and/or a sulfonic acid. The reaction may be
enhanced by heating the reaction mixture (with or without a catalyst) to
a temperature in the range from about 100° C. to about 250°
C., or from about 150° C. to about 200° C.

[0453] The amount of catalyst added to the reaction may be from about 0.01
percent by weight to about 5 percent by weight of the functionalized
monomer, polymer or copolymer, or mixture of functionalized monomer,
polymer or copolymer, and alkenylsuccinic acid or anhydride, in the
reaction mixture, or from about 0.5 percent by weight to about 2 percent
by weight.

[0454] The reaction may be conducted in an inert atmosphere, for example,
a nitrogen atmosphere. The time of reaction may range from about 3 to
about 24 hours, or from about 8 to about 12 hours.

[0455] The dispersants may be post-treated/post-reacted by conventional
methods using any of a variety of agents. Among these may be boron
compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles,
carbon disulfide, aldehydes, ketones, carboxylic acids such as
terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic
anhydride, nitriles, epoxides, phosphorus compounds, and the like.

Detergents

[0456] The functionalized or polyfunctionalized monomer, polymer or
copolymer of the invention may be used to produce a neutral or overbased
product or material which may be used as a detergent in a lubricant or
functional fluid composition. The detergent may comprise a neutral or
overbased material derived from a metal or metal compound, and: (i) a
functionalized monomer comprising a hydrocarbyl group with one or more
carbon-carbon double bonds and one or more functional groups attached to
the hydrocarbyl group, the hydrocarbyl group containing from about 5 to
about 30 carbon atoms, or from about 6 to about 30 carbon atoms, or from
about 8 to about 30 carbon atoms, or from about 10 to about 30 carbon
atoms, or from about 12 to about 30 carbon atoms, or from about 14 to
about 30 carbon atoms, or from about 16 to about 30 carbon atoms, or from
about 5 to about 18 carbon atoms, or from about 12 to about 18 carbon
atoms, or about 18 carbon atoms, the functional group comprising a
carboxylic acid group or derivative thereof; (ii) a polymer derived from
one or more of the functionalized monomers (i); (iii) a copolymer derived
from one or more of the functionalized monomers (i) and one or more
olefin comonomers; (iv) the reaction product of an enophilic acid reagent
with the monomer (i), polymer (ii) and/or copolymer (iii); or (v) a
mixture of two or more of (i), (ii), (iii) and (iv). The olefin comonomer
may contain from 2 to about 30 carbon atoms, or from about 6 to about 24
carbon atoms. The polymer or copolymer may contain at least about 30 mole
percent of repeating units derived from the functionalized or
polyfunctionalized monomer, or at least about 50 mole percent, or at
least about 70 mole percent, or from about 30 to about 100 mole percent,
or from about 50 to about 100 percent, or from about 70 to about 100 mole
percent. The enophilic acid reagent may comprise one or more alpha-beta
unsaturated carboxylic acids and/or derivatives thereof. The monomer (i),
polymer (ii), copolymer (iii) and/or reaction product (iv), may be mixed
with an alkarylsulfonic acid (e.g., alkylbenzenesulfonic acid) prior to
or during the reaction to form the overbased material. The functionalized
or polyfunctionalized polymer or copolymer may have a number average
molecular weight in the range from about 300 to about 50,000, or from
about 300 to about 20,000, or from about 300 to about 10,000, or from
about 500 to about 3000, as determined by gel permeation chromatography
(GPC), NMR spectroscopy, vapor phase osometry (VPO), wet analytical
techniques such as acid number, base number, saponification number of
oxirane number, and the like. The polymer or copolymer may be prepared
using the procedures described above.

[0457] The term "overbased" is a term of art which is generic to well
known classes of metal salts or complexes. These products or materials
have also been referred to as "basic", "superbased", "hyperbased",
"complexes", "metal complexes", "high-metal containing salts", and the
like. Overbased products or materials may be regarded as metal salts or
complexes characterized by a metal content in excess of that which would
be present according to the stoichiometry of the metal and the particular
acidic organic compound, e.g., a carboxylic acid, reacted with the metal.
Thus, if a monocarboxylic acid,

RCOOH

is neutralized with a basic metal compound, e.g., calcium hydroxide, the
"neutral" or "normal" metal salt produced will contain one equivalent of
calcium for each equivalent of acid, i.e.,

R--C(═O)--O--Ca--O--C(═O)--R

However, various processes may be used to produce an inert organic liquid
solution of a product containing more than the stoichiometric amount of
metal. This solution may be referred to as overbased product or material.
Following these procedures, the carboxylic acid may be reacted with a
metal base. The resulting product may contain an amount of metal in
excess of that necessary to neutralize the acid. For example, 4 times as
much metal as present in the neutral salt, or a metal excess of 3
equivalents, may be used. The actual stoichiometric excess of metal may
vary considerably, for example, from about 0.1 equivalent to about 40 or
more equivalents depending on the reactions, the process conditions, and
the like. An equivalent of a metal is dependent upon its valence, and the
nature/structure of the functional group in the substrate. Thus, for a
reaction with a substrate, such as a monocarboxylic acid, one mole of a
monovalent metal such as sodium provides one equivalent of the metal,
whereas 0.5 moles of a divalent metal such as calcium are required to
provide one equivalent of such metal. The number of equivalents of a
metal base in a detergent can be measured using standard techniques
(e.g., titration using bromophenol blue as the indicator to measure total
base number, TBN).

[0458] The term "metal ratio" is used herein to designate the ratio of the
total chemical equivalents of the metal in the overbased material (e.g.,
a metal carboxylate) to the chemical equivalents of the metal in the
product which would be expected to result from the reaction between the
organic material to be overbased (e.g., carboxylic acid) and the
metal-containing reactant (e.g., calcium hydroxide, barium oxide, etc.)
according to the known chemical reactivity and stoichiometry of the two
reactants. Thus, in the normal or neutral calcium carboxylate discussed
above, the metal ratio is one, and in the overbased carboxylate, the
metal ratio is 4, or more. If there is present in the material to be
overbased more than one compound capable of reacting with the metal, the
"metal ratio" of the product will depend upon whether the number of
equivalents of metal in the overbased product is compared to the number
of equivalents expected to be present for a given single component or a
combination of all such components.

[0459] The neutral or overbased product or material useful as a detergent
may be neutral or may be overbased with a metal ratio in excess of 1 and
generally up to about 40 or more. The metal ratio may be in the range
from an excess of 1 up to about 35, or from an excess of 1 up to about
30. The metal ratio may range from about 1.1 or about 1.5 to about 40; or
from about 1.1 or about 1.5 to about 35; or from about 1.1 or about 1.5
to about 30; or from about 1.1 or about 1.5 to about 25. The metal ratio
may range from about 1.5 to about 30 or 40, or from about 5 to about 30
or 40, or from about 10 to about 30 or 40, or from about 15 to about 30
or 40. The metal ratio may range from about 20 to about 30.

[0460] The overbased product or material may be prepared using the
functionalized monomer (i), polymer (ii), copolymer (iii) and/or reaction
product (iv) of the invention, alone or in combination with an
alkarylsulfonic acid. The monomer (i), polymer (ii), copolymer (iii),
and/or reaction product (iv) and, optionally, the alkarylsulfonic acid,
may be referred to herein as (1) the organic material to be overbased.
The overbased product or material may be prepared by the reaction of a
mixture of (1) the organic material to be overbased, (2) a reaction
medium comprising an inert, organic solvent/diluent for the organic
material to be overbased, a stoichiometric excess of (3) at least one
metal base, and (4) a promoter, with (5) an acidic material. The
overbased product or material may be borated by reacting the overbased
product or material with a boron containing compound.

[0461] The alkarylsulfonic acids may include alkylbenzenesulfonic acids
wherein the alkyl group contains at least about 8 carbon atoms, or from
about 8 to about 30 carbon atoms. The ratio of equivalents of the
functionalized monomer (i), polymer (ii), copolymer (iii) and/or reaction
product (iv) to the alkarylsulfonic acid may be from about 1 to about 5,
or from about 1 to about 2. The weight of an equivalent of an
alkarylsulfonic acid agent is dependent on the number of sulfonic acid
groups in the alkarylsulfonic acid that are reactive with the metal base
(3). For example, one mole of an alkarylsulfonic acid having one sulfonic
acid available for reaction with the metal base would have an equivalent
weight equal to the molecular weight of the alkarylsulfonic acid.

[0462] The organic material to be overbased (1) may be soluble in the
reaction medium (2). When the reaction medium (2) is a petroleum fraction
(e.g., mineral oil), the organic material to be overbased may be
oil-soluble. However, if another reaction medium is employed (e.g.,
aromatic hydrocarbons, aliphatic hydrocarbons, kerosene, etc.) the
organic material to be overbased (1) may not necessarily be soluble in
mineral oil as long as it is soluble in the given reaction medium. When
referring to the solubility of the (1) organic material to be overbased
in (2) the reaction medium, it is to be understood that the organic
material to be overbased may be soluble in the reaction medium to the
extent of at least one gram of the material to be overbased per liter of
reaction medium at 20° C.

[0464] Also useful as the reaction medium (2) may be low molecular weight
liquid polymers, generally classified as oligomers, which may include
dimers, trimers, tetramers, pentamers, etc. Illustrative of this class of
materials may be such liquids as propylene tetramers, isobutylene dimers,
and the like.

[0465] The metal base (3) used in preparing the neutral or overbased
products or materials may comprise one or more alkali metals,
alkaline-earth metals, titanium, zirconium, molybdenum, iron, copper,
zinc, aluminum, mixture of two or more thereof, or basically reacting
compounds thereof. Lithium, sodium, potassium, magnesium, calcium,
strontium, barium, zinc, or a mixture of two or more thereof, may be
useful.

[0466] The basically reacting compound may comprise any compound of any of
the foregoing metals or mixtures of metals that is more basic than the
corresponding metal salt of the acidic material (5) used in preparing the
overbased product or material. These compounds may include hydroxides,
alkoxides, nitrites, carboxylates, phosphites, sulfites, hydrogen
sulfites, carbonates, hydrogen carbonates, borates, hydroxides, oxides,
alkoxides, amides, etc. The nitrites, carboxylates, phosphites,
alkoxides, carbonates, borates, hydroxides and oxides may be useful. The
hydroxides, oxides, alkoxides and carbonates may be useful.

[0467] The promoters (4), that is, the materials which facilitate the
incorporation of an excess metal into the overbased product may include
those materials that are less acidic than the acidic material (5) used in
making the overbased products. These may include alcoholic and phenolic
promoters. The alcohol promoters may include alkanols of one to about 12
carbon atoms. Phenolic promoters may include a variety of
hydroxy-substituted benzenes and naphthalenes. The phenolic promoters may
include alkylated phenols such as heptylphenol, octylphenol, nonylphenol,
dodecyl phenol, propylene tetramer phenol, and mixtures of two or more
thereof.

[0469] The acidic material (5) may comprise one or more of carbamic acid,
acetic acid, formic acid, boric acid, trinitromethane, SO2,
CO2, sources of said acids, and mixtures thereof. CO2 and
SO2, and sources thereof, are preferred. Sources of CO2 may
include ammonium carbonate and ethylene carbonate. Sources of SO2
may include sulfurous acid, thiosulfuric acid, dithionous acid, and/or
their salts.

[0470] The overbased products or materials may be prepared by reacting a
mixture of the organic material to be overbased, the reaction medium, the
metal base, and the promoter, with the acidic material. A chemical
reaction may then ensue. The temperature at which the acidic material
reacts with the remainder of the reaction mass may depend upon the
promoter that is used. With a phenolic promoter, the temperature may
range from about 60° C. to about 300° C., or from about
100° C. to about 200° C. When an alcohol or mercaptan is
used as the promoter, the temperature may not exceed the reflux
temperature of the reaction mixture. The exact nature of the resulting
overbased product or material may not be known. However, it may be
described for purposes of the present specification as a single phase
homogeneous mixture of the reaction medium and either a metal complex
formed from the metal base, the acidic material, and the organic material
to be overbased and/or an amorphous metal salt formed from the reaction
of the acidic material with the metal base and the organic material to be
overbased.

[0472] The reaction of the overbased product with the boron compound can
be effected using standard mixing techniques. The ratio of equivalents of
the boron compound to equivalents of the overbased product may range up
to about 40:1 or higher, or in the range of about 0.05:1 to about 30:1,
or in the range of about 0.2:1 to about 20:1. Equivalent ratios of about
0.5:1 to about 5:1, or about 0.5:1 to about 2:1, or about 1:1 may be
used. An equivalent of a boron compound may be based upon the number of
moles of boron in the compound. Thus, boric acid has an equivalent weight
equal to its molecular weight, while tetraboric acid has an equivalent
weight equal to one-fourth of its molecular weight. An equivalent weight
of an overbased product or material is based upon the number of
equivalents of metal in the overbased product available to react with the
boron. Thus, an overbased product having one equivalent of metal
available to react with the boron has an equivalent weight equal to its
actual weight. An overbased product having two equivalents of metal
available to react with the boron has an equivalent weight equal to
one-half its actual weight. The temperature can range from about room
temperature up to the decomposition temperature of the reactants or
desired products having the lowest such temperature, and may be in the
range of about 20° C. to about 200° C., or about 20°
C. to about 150° C., or about 50° C. to about 150°
C., or about 80° C. to about 120° C. The reaction time may
be the time required to form the desired concentration of metal borate
(e.g., sodium borate) in the boron-containing overbased product. The
reaction time may be from about 0.5 to about 50 hours, or from about 1 to
about 25 hours, or about 1 to about 15 hours, or about 4 to about 12
hours.

The Lubricant and Functional Fluid Compositions

[0473] The lubricant and/or functional fluid compositions of the invention
may comprise a base oil comprising a polymer or copolymer derived from
one or more of the above-identified functionalized monomers,
polyfunctionalized monomers, polymers and/or polyfunctionalized polymers.
The dispersants and/or detergents described above, which may be derived
from one or more of the above-identified functionalized monomers,
polyfunctionalized monomers, polymers and/or polyfunctionalized polymers
may be used in these lubricants and/or functional fluids.

[0475] In an embodiment, the base oil may comprise a polymer derived from
one or more of the above-identified functionalized or polyfunctionalized
monomers. The polymer or copolymer may have a number average molecular
weight in the range from about 300 to about 50,000, or from about 300 to
about 20,000, as determined by GPC. The polymer or copolymer may be used
alone as the base oil or it may be blended with an American Petroleum
Institute (API) Group II, III, IV or V base oil or a biologically derived
oil. Examples of the biologically derived oil may include soybean oil,
rapeseed oil, and the like. The blended base oil may contain from about
1% to about 75%, or from about 5% to about 60% by weight of the polymer
or copolymer. The lubricant or functional fluid containing this base oil
may further comprise one or more of the above-identified dispersants
and/or detergents. The dispersant may be present in the lubricant or
functional fluid composition at a concentration in the range from about
0.01 to about 20% by weight, or from about 0.1 to about 15% by weight
based on the weight of the lubricant or functional fluid. The detergent
may be present in the lubricant or functional fluid composition at a
concentration in the range from about 0.01% by weight to about 50% by
weight, or from about 1% by weight to about 30% by weight based on the
weight of the lubricant or functional fluid composition. The detergent
may be present in an amount suitable to provide a TBN (total base number)
in the range from about 2 to about 100 to the lubricant composition, or
from about 3 to about 50. TBN is the amount of acid (perchloric or
hydrochloric) needed to neutralize all or part of a material's basicity,
expressed as milligrams of KOH per gram of sample. These lubricants or
functional fluids may be useful as fill-for-life fluids.

[0476] In an embodiment, the base oil may comprise a copolymer derived
from the above-identified functionalized or polyfunctionalized monomer
and an olefin comonomer. The copolymer may contain from about 5 to about
30 mole percent, or from about 10 to about 25 mole percent, repeating
units derived from the functionalized or polyfunctionalized monomer. The
copolymer may have a number average molecular weight in the range from
about 300 to about 50,000, or from about 300 to about 20,000, as
determined by GPC. The copolymer may be used alone or it may be blended
with an API Group I, Group II, Group III and/or Group IV base oil. The
amount of copolymer in the blended base oil may range from about 1% to
about 50% by weight, or from about 5% to about 25% by weight. The
lubricant or functional fluid may further comprise one or more of the
above-identified dispersants and/or detergents. The dispersant may be
present in the lubricant or functional fluid composition at a
concentration in the range from about 0.01 to about 20% by weight, or
from about 0.1 to about 15% by weight based on the weight of the
lubricant or functional fluid. The detergent may be present in the
lubricant or functional fluid composition at a concentration in the range
from about 0.1% by weight to about 50% by weight, or from about 1% by
weight to about 30% by weight based on the weight of the lubricant or
functional fluid composition. The detergent may be present in an amount
suitable to provide a TBN in the range from about 2 to about 100 to the
lubricant or functional fluid composition, or from about 3 to about 50.

[0477] The API Group I-V base oils have the following characteristics:

TABLE-US-00005
Base Oil
Category Sulfur (%) Saturates (%) Viscosity Index
Group I >0.03 and/or <90 80 to 120
Group II ≦0.03 and ≧90 80 to 120
Group III ≦0.03 and ≧90 ≧120
Group IV All polyalphaolefins (PAO)
Group V All others not included in Groups I, II, III, or IV

The Group I-III base oils are mineral oils.

[0478] The base oil (i.e., polymer or polymer blended with API Group I-V
base oil) may have a viscosity up to about 35 cSt at 100° C., or
in the range from about 3 to about 35 cSt at 100° C., or about 5
to about 20 cSt at 100° C. The base oil may be present in the
lubricant or functional fluid composition at a concentration of greater
than about 60% by weight based on the overall weight of the lubricant or
functional fluid composition, or greater than about 65% by weight, or
greater than about 70% by weight, or greater than about 75% by weight.

[0479] The lubricant or functional fluid composition may include one or
more additional functional additives, including, for example, one or more
supplemental detergents and/or dispersants, as well as corrosion- and
oxidation-inhibiting agents, pour point depressing agents, extreme
pressure (EP) agents, antiwear agents, color stabilizers, viscosity
modifiers, demulsifiers, seal swelling agents, anti-foam agents, mixtures
of two or more thereof, and the like.

[0480] The supplemental detergent may include one or more overbased
materials prepared by reacting an acidic material (typically an inorganic
acid or lower carboxylic acid, such as carbon dioxide) with a mixture
comprising an acidic organic compound, a reaction medium comprising at
least one inert, organic solvent (mineral oil, naphtha, toluene, xylene,
etc.) for said acidic organic material, a stoichiometric excess of a
metal base, and a promoter such as a calcium chloride, acetic acid,
phenol or alcohol. The acidic organic material may have a sufficient
number of carbon atoms to provide a degree of solubility in oil. The
metal may be zinc, sodium, calcium, barium, magnesium, or a mixture of
two or more thereof. The metal ratio may be from an excess of 1 to about
40.

[0481] The supplemental dispersants that may be used may include any
dispersant known in the art which may be suitable for the lubricant or
functional fluid compositions of this invention. These may include:

[0482] (1) Reaction products of carboxylic acids (or derivatives thereof),
with nitrogen containing compounds such as amines, hydroxy amines,
organic hydroxy compounds such as phenols and alcohols, and/or basic
inorganic materials. These may be referred to as carboxylic dispersants.
These may include succinimide dispersants, such as
polyisobutenylsuccinimide.

[0483] (2) Reaction products of relatively high molecular weight aliphatic
or alicyclic halides with amines, for example, polyalkylene polyamines.
These may be referred to as "amine dispersants."

[0484] (3) Reaction products of alkylphenols with aldehydes (e.g.,
formaldehyde) and amines (e.g., polyalkylene polyamines), which may be
referred to as "Mannich dispersants."

[0486] (5) Interpolymers of oil-solubilizing monomers such as decyl
methacrylate, vinyl decyl ether and high molecular weight olefins with
monomers containing polar substituents, e.g., aminoalkyl acrylates or
acrylamides and poly-(oxyethylene)-substituted acrylates. These may be
referred to as "polymeric dispersants."

[0488] Many of the above-mentioned extreme pressure agents and
corrosion-oxidation inhibitors may also serve as antiwear agents. Zinc
dialkyl phosphorodithioates are examples of such multifunctional
additives.

[0489] Pour point depressants may be used to improve low temperature
properties of the oil-based compositions. Examples of useful pour point
depressants may include polymethacrylates; polyacrylates;
polyacrylamides; condensation products of haloparaffin waxes and aromatic
compounds; vinyl carboxylate polymers; and terpolymers of dialkyl
fumarates, vinyl esters of fatty acids, alkyl vinyl ethers, or mixtures
of two or more thereof.

[0490] The viscosity modifiers may include one or more polyacrylates,
polymethacrylates, polyolefins, and/or styrene-maleic ester copolymers.

[0491] Anti-foam agents may be used to reduce or prevent the formation of
stable foam. The anti-foam agents may include silicones, organic
polymers, and the like.

[0492] The lubricant or functional fluid may include one or more
thickeners to provide the lubricant or functional fluid with a
grease-like consistency. The thickener may comprise lithium hydroxide,
lithium hydroxide monohydrate, or a mixture thereof.

[0493] The functional additives may be added directly to the lubricant or
functional fluid composition. Alternatively, the additives may be diluted
with a substantially inert, normally liquid organic diluent such as
mineral oil, naphtha, benzene, toluene or xylene, to form an additive
concentrate, which may then be added to the lubricant and/or functional
fluid. These concentrates may contain from about 0.1 to about 99%, or
from about 10% to about 90% by weight, of one or more of the additives.
The remainder of the concentrate may comprise the substantially inert
normally liquid diluent.

The Fuel Composition

[0494] The fuel composition may contain a major proportion of a normally
liquid fuel. The normally liquid fuel may comprise motor gasoline or a
middle distillate fuel. The middle distillate fuel may comprise diesel
fuel, fuel oil, kerosene, jet fuel, heating oil, naphtha, or a mixture of
two or more thereof. The fuel composition may also comprise one or more
non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro
compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl
ethyl ether, nitromethane). Normally liquid fuels which are mixtures of
one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous
materials may be used. Examples of such mixtures may include combinations
of gasoline and ethanol, or combinations of diesel fuel and ether.
Gasoline may comprise a mixture of hydrocarbons having an ASTM
distillation range from about 60° C. at the 10% distillation point
to about 205° C. at the 90% distillation point.

[0495] The normally liquid fuel may comprise a natural oil, including
vegetable oil, animal fat or oil, or a mixture thereof. These may be
referred to as biofuels or biodiesel fuels. The normally liquid fuel may
comprise a hydrocarbon oil (e.g., a petroleum or crude oil distillate).
The fuel may comprise a mixture of a hydrocarbon oil and a natural oil.

[0496] The normally liquid fuel may comprise a synthetic fuel. The
synthetic fuel may be derived from coal, natural gas, oil shale, biomass,
or a mixture of two or more thereof. The synthetic fuel may be derived
from a Fischer-Tropsch process.

[0497] The fuel composition may contain a property improving amount of one
or more of the above-described dispersants. This amount may be from about
10 to about 1000 parts by weight, or from about 100 to about 500 parts by
weight, of the dispersant per million parts of the normally liquid fuel.

[0498] The fuel composition may contain other additives well known to
those of skill in the art. These may include deposit preventers or
modifiers such as triaryl phosphates, dyes, cetane improvers,
antioxidants such as 2,6-di-tertiary-butyl-4-methyl-phenol, rust
inhibitors such as alkenylsuccinic acids and anhydrides, bacteriostatic
agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder
lubricants, anti-icing agents, mixtures of two or more thereof, and the
like.

[0500] The following examples illustrate features in accordance with the
present invention, and are provided solely by way of illustration. They
are not intended to limit the scope of the appended claims.

Example 1

Methyl 9-Decenoate Homopolymer Using t-Bu2O2

[0501] Methyl 9-decenoate (50 g, 0.271 mole) and di-t-butyl peroxide (4 g,
0.0271 mole) are charged into a reaction flask that is equipped with a
thermometer, nitrogen inlet, magnetic stirrer, and reflux condenser. The
resulting reaction mixture is heated to 130° C. An exotherm occurs
and the temperature of the reaction mixture increases to 160° C.
The exotherm subsides over time and the reaction temperature is dropped
to 130° C. Heating is continued at 120-130° C. for 6.5 hrs.
An additional amount of di-t-butyl peroxide (4 g, 0.0271 mole) is added
and the reaction mixture is heated for an additional time of 5 hrs. The
reaction mixture is then stripped to 150° C. using vacuum of 2
torr (0.27 kilopascal). Residue left after stripping, which is in the
form of a viscous fluid, is the desired product. The amount of desired
product is 40 g (80% yield).

Example 2

9-Decenoic Acid Homopolymer

[0502] 9-Decenoic acid (100 g, 0.59 mole) and di-t-butyl peroxide (8.6 g,
0.06 mole) are charged into a 2-necked 250-mL flask that is equipped with
a magnetic stirrer, Dean-Stark trap, nitrogen inlet, thermometer, and
reflux condenser. The reaction mixture is heated to 130° C. An
exotherm occurs and the temperature of the reaction mixture increases to
157° C. The exotherm subsides over time and the reaction
temperature drops to 130° C. Heating is continued at
120-130° C. for 6.5 hrs. The reaction mixture is then stripped at
150-180° C. using a vacuum of 2 torr (0.27 kilopascal). Residue
left after stripping, which is in the form of a viscous fluid, is the
desired product. The amount of desired product is 55 g (55% yield). The
product has an acid number of 314 mg KOH/g.

Example 3

Homopolymerization of Pentaerythritol Ester of 9-Decenoic Acid by the Use
of t-Bu2O2

[0503] Pentaerythritol ester of 9-decenoic acid (30 g, 0.04 mole) is
charged into a 3-necked 100-mL flask that is equipped with a magnetic
stirrer, nitrogen inlet, thermometer, and a reflux condenser. The ester
is heated to 150° C. and di-t-butyl peroxide (0.64 g, 0.0046 mole)
is added in two portions, 30 minutes apart. The reaction mixture is
heated at 150° C. for 1 hr. The viscosity of the reaction mixture
increases and polymer is formed.

Example 4

Copolymerization of 1-Decene and Pentaerythritol Ester of 9-Decenoic Acid
by the Use of t-Bu2O2

[0504] 1-Decene (200 g, 1.43 moles) and pentaerythritol ester of
9-decenoic acid (40 g, 0.053 mole) are charged into a 3-necked 500-mL
flask that is equipped with a magnetic stirrer, nitrogen inlet,
thermometer, and reflux condenser. Di-t-butyl peroxide (20.8 g, 0.142
mole) is added in five portions that are 30 minutes apart. The reaction
mixture is heated at 130° C. for 10 hr. Distillation is then
carried out to remove unreacted decene (122 g), leaving behind 130 g of a
copolymer in the form of a clear viscous fluid.

Example 5

Copolymerization of 1-Decene and Methyl 9-Decenoate by the Use of
t-Bu2O2

[0505] 1-Decene (250 g, 1.786 mole), and methyl 9-decenoate (33 g, 0.179
mole) are charged into a 3-necked 500-mL flask that is equipped with a
magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, and
reflux condenser. The reaction mixture is brought to 150° C. and
di-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30
minutes apart. The reaction mixture is heated at 150° C. for a
total of 10 hr. Distillation is then carried out to remove the starting
material and low-boiling components, leaving behind 198 g of a clear
viscous product (70% conversion).

Example 6

Copolymerization of 1-Decene and 9-Decenoic Acid by the Use of
t-Bu2O2

[0506] 1-Decene (200 g, 1.43 moles), and 9-decenoic acid (27 g, 0.159
mole) are charged into a 3-necked 500-mL flask that is equipped with a
magnetic stirrer, nitrogen inlet, thermometer, and reflux condenser. The
reaction mixture is brought to 150° C. and di-t-butyl peroxide
(23.2 g, 0.159 mole) is added in six portions that are 30 minutes apart.
The reaction mixture is heated at 140° C. for 3 hr. Distillation
is then carried out to remove the starting material and the low-boiling
components, leaving behind a clear viscous product that has an acid
number of 60.

Example 7

Dispersants Derived from 1-Decene/9-Decenoic Acid Polymer

[0507] 1-Decene (200 g, 1.43 moles), and 9-decenoic acid (27 g, 0.159
mole) are charged into a 3-necked 500-mL flask that is equipped with a
magnetic stirrer, nitrogen inlet, thermometer, and reflux condenser. The
reaction mixture is brought to 170° C. and di-t-amyl peroxide
(27.5 g, 0.159 mole) is added in six portions that are 30 minutes apart.
The reaction mixture is heated at 150° C. for a total of 6.5 hr.
Distillation is carried out to remove the starting material and the
low-boiling components, leaving behind a clear viscous product that has
an acid number of 56.

[0508] A first dispersant is made by reacting 50 g of the
1-decene/9-decenoic acid polymer with diethylenetriamine at 150°
C. The carboxylic acid to nitrogen ratio is 2:3. The reaction mixture is
held at this temperature until the acid number of the mixture is 10. A
small amount of toluene is used in the reaction to remove water of
reaction. Toluene is removed at the end of reaction.

[0509] A second dispersant is made by reacting 50 g of the
1-decene/9-decenoic acid polymer with pentaerythritol at 150° C.
The carboxylic acid to hydroxyl ratio is 4:1. The reaction is continued
until an acid number of 10 is achieved. A small amount of toluene is used
in the reaction to remove water of reaction. Toluene is removed at the
end of reaction.

[0510] Both the first and second dispersants have good American Petroleum
Institute (API) Group I oil and Group II oil miscibility at 20 percent
and 50 percent by weight.

Example 8

Polymerization of Methyl 9-Decenoate by the Use of an Acid Catalyst
(Montmorillonite K10)

[0511] Methyl 9-decenoate (250 g) and Montmorillonite K10 (50 g) are
placed in a glass liner. The glass liner is inserted in a Parr reaction
vessel. The vessel is sealed, purged with N2 for 15 minutes, and an
initial N2 pressure of 8 psi (55.2 kilopascals) is applied. The
mixture is heated to 200° C. with 600 rpm stirring. The reaction
mixture reaches the desired temperature in 30 minutes. The reaction
mixture is stirred at this temperature for 8 hours. The final pressure is
135 psi (930.8 kilopascals). The reaction mixture is hot-filtered to
remove the catalyst. The filtrate is subjected to vacuum distillation at
190° C. and 20 mmHg (2.67 kilopascals). The distillation residue
(130 g) is the desired product. The average molecular weight is about
500.

Example 9

Polymerization of 1-Decene-Methyl 9-Decenoate Mixture by the Use of an
Acid Catalyst (Montmorillonite K10)

[0512] 1-Decene (140 g, 1 mole), methyl 9-decenoate (184 g, 1 mole), and
Montmorillonite K10 (50 g) are placed in a glass liner which is inserted
in a Parr reaction vessel. The vessel is sealed, purged with N2 for
15 minutes, and an initial N2 pressure of 8 psi (55.2 kilopascals)
is applied. The mixture is heated at 250° C. with 600 rpm stirring
for 11 hours. The final pressure is 135 psi (930.8 kilopascals). The
reaction mixture is hot-filtered to remove the catalyst. The filtrate is
subjected to vacuum distillation at 190° C. and 20 mmHg (2.67
kilopascals). TLC and GC/MS indicate the presence of copolymer.

Example 10

Copolymerization of 1-Hexene and Methyl 9-Decenoate by the Use of
t-Bu2O2

Copolymerization of Dodecene and Methyl 9-Octadecenedioate by the Use of
t-Bu2O2

[0519] 1-Dodecene (300 g, 1.786 mole), and methyl 9-octadecenedioate (63.6
g, 0.179 mole) are charged into a 3-necked 500-mL flask that is equipped
with a magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap,
and reflux condenser. The reaction mixture is brought to 130° C.
and di-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30
minutes apart. The reaction mixture is heated at 130° C. for 10
hours. After this time, distillation is carried out to remove the
starting material and low-boiling components, leaving behind the desired
product.

Example 17

Methyl 9-Decenoate Homopolymer Using t-Bu2O2

[0520] Methyl 9-decenoate (35 g, 0.271 mole) and di-t-butyl peroxide (4 g,
0.0271 mole) are charged into a reaction flask that is equipped with a
thermometer, nitrogen inlet, magnetic stirrer, and reflux condenser.
Reaction mixture is heated to 130° C. An exotherm occurs and the
temperature of the reaction mixture rises to 160° C. The exotherm
subsides over time and the reaction temperature drops to 130° C.
Heating is continued at 120-130° C. for 6.5 hrs. An additional
amount of di-t-butyl peroxide (4 g, 0.0271 mole) is added and the
reaction mixture is heated for an additional time of 5 hrs. The reaction
mixture is then stripped to 150° C. using vacuum of 2 torr (0.27
kilopascal) to yield product in the form of a viscous fluid.

Example 18

5-Hexenoic Acid Homopolymer Using t-Bu2O2

[0521] 5-Hexenoic acid (67 g, 0.59 mole) and di-t-butyl peroxide (8.6 g,
0.06 mole) are charged into a 2-necked 250-mL flask that is equipped with
a magnetic stirrer, Dean-Stark trap, nitrogen inlet, thermometer, and
reflux condenser. The reaction mixture is heated to 130° C. An
exotherm occurs and the temperature of the reaction mixture rises to
150° C. The exotherm subsides over time and the reaction
temperature drops to 130° C. Heating is continued at
120-130° C. for 6.5 hrs. The reaction mixture is then stripped at
150-180° C. using vacuum of 2 torr (0.27 kilopascals). Residue
left after stripping, which is in the form of a viscous fluid, is the
desired product.

Example 19

Methyl Octadecenoate Homopolymer Using t-Bu2O2

[0522] Methyl octadecenoate (81 g) and di-t-butyl peroxide (4 g) are
charged into a reaction flask that is equipped with a thermometer,
nitrogen inlet, magnetic stirrer, and reflux condenser. The reaction
mixture is heated to 130° C. An exotherm occurs and the
temperature of the reaction mixture rises to 160° C. The exotherm
subsides over time and the reaction temperature drops to 130° C.
Heating is continued at 120-130° C. for 6.5 hrs. An additional
amount of di-t-butyl peroxide (4 g, 0.0271 mole) is added and the
reaction mixture is heated for an additional time of 5 hrs. The reaction
mixture is then stripped to 150° C. using a vacuum of 2 torr (0.27
kilopascals) to yield the desired product which is in the form of a
viscous fluid.

Example 20

Octadecenoic Acid Homopolymer Using t-Bu2O2

[0523] Octadecenoic acid (79 g) and di-t-butyl peroxide (8.6 g) are
charged into a 2-necked 250-mL flask that is equipped with a magnetic
stirrer, Dean-Stark trap, nitrogen inlet, thermometer, and reflux
condenser. The reaction mixture is heated to 130° C. An exotherm
occurs and the temperature of the reaction mixture rises to 150°
C. The exotherm subsides over time and the reaction temperature drops to
130° C. Heating is continued at 120-130° C. for 6.5 hrs.
The reaction mixture is then stripped at 150-180° C. using vacuum
of 2 torr (0.27 kilopascals). Residue left after stripping, which is in
the form of a viscous fluid, is the desired product.

[0524] A 1-litre round-bottomed flask is charged with 400 g of a solution
of 75% polymer composition, prepared from a free radical polymerization
of 1-decene:9-decenoic acid (75:25) mole percent mixture, in xylenes. The
contents of the flask are then heated with stirring to 175° C.
Aminopropylimidazole (38 g) is added dropwise via a pressure equalizing
dropping funnel over a period of 30 minutes. The reaction mixture is then
maintained at 175° C. with stirring and water removal for 3 hours.
Solvent and low-boiling volatiles are removed via distillation, leaving
behind an amber viscous product that is filtered through a 12 mm Celite
pad.

Example 22

Imide Dispersant Preparation from Methyl 9-Decenoate Homopolymer

[0525] A mixture of 500 g of homopolymer and 30 g of maleic anhydride is
heated to 110° C. This mixture is heated to 200° C. and is
held there for 6 hr. The reaction mixture is then stripped of starting
materials, leaving behind succinated homopolymer. To this material is
added 113 g of mineral oil, and 10 g of a commercial mixture of ethylene
polyamines having from about 3 to about 10 nitrogen atoms per molecule.
The reaction mixture is heated to 150° C. for 2 hr and is stripped
by blowing with nitrogen. The reaction mixture is filtered to yield the
filtrate as an oil solution of the desired product.

Example 23

Dispersant Preparation from Methyl 9-Decenoate Homopolymer

[0526] A mixture of 500 g of methyl 9-decenoate homopolymer and 30 g of
maleic anhydride is heated to 110° C. This mixture is heated to
200° C. and is held there for 6 hr. After this time the reaction
is stripped of starting materials, leaving behind succinated homopolymer.
To this material is added 30 g of pentaerythritol and the reaction
mixture is heated to 210° C. and held at this temperature for 3
hr. The reaction mixture is cooled to 190° C. and 8 g of a
commercial mixture of ethylene polyamines having an average of about 3 to
about 10 nitrogen atoms per molecule is added. The reaction mixture is
stripped by heating at 205° C. with nitrogen blowing for 3 hours,
then filtered to yield the filtrate as an oil solution of the desired
product.

[0527] A mixture of 200 g of mineral oil, 30 g polyisobutenylsuccinic acid
anhydride, 50 g of a mixture of 61% by weight isobutanol and 39% by
weight amyl alcohol, and Mississippi Lime (86% available Ca) are charged
to a stainless steel reactor having a stirrer, condenser, and an oil
system to a jacket around the reactor for both heating and cooling. With
stirrer agitation of the mixture and a nitrogen gas purge above the
reaction mixture, 200 g of 1-decene/1-decenoic acid polymer composition,
prepared from free radical polymerization of 1-decene:9-decenoic acid
(75:25) mole percent mixture. The mixture is then heated to 90° C.
to complete the acid and acid anhydride neutralization. 25 g methanol and
140 g of the above-mentioned Mississippi Lime are added after cooling the
batch to 40° C. The material in the reaction vessel is carbonated
at 50-60° C. by passing carbon dioxide into the reaction mixture
until the reaction mixture has a base number of approximately zero. After
carbonation, the material is flash dried to remove the alcohol promoters
and water by raising the temperature to 150° C. and purging with
nitrogen gas. The material is then cooled, solvent clarified by adding
approximately 150 parts hexane, and vacuum stripped of volatiles to
150° C. and 70 mm absolute Hg. The product is filtered and diluent
oil is added to adjust calcium content to 14.2 percent by weight calcium.

[0528] To a solution of 100 g of an alkylbenzenesulfonic acid, 100 g of
methyl 9-decenoate homopolymer, 10 g of polyisobutenylsuccinic anhydride,
and 50 g mineral oil is added 100 g of calcium hydroxide, and 50 g of a
mixture of 61 percent by weight isobutanol and 39 percent by weight amyl
alcohol. The temperature of the mixture increases to 89° C. over
10 minutes due to an exotherm. During this period, the mixture is blown
with carbon dioxide at 4 cubic feet/hr (cfh) (113.3 liters per hour).
Carbonation is continued for about 30 minutes as the temperature
gradually decreases to 74° C. The alcohols and other volatile
materials are stripped from the carbonated mixture by blowing nitrogen
through it at 2 cfh (56.6 liters per hour) while the temperature is
slowly increased to 150° C. over 90 minutes. After stripping is
completed, the remaining mixture is held at 155-165° C. for about
30 minutes and filtered to yield an oil solution of the desired basic
detergent.

[0529] Table 1 below shows data for homopolymers and various polymer
compositions prepared using monomers in accordance with the present
teachings.

[0530] While the invention has been explained in relation to various
embodiments, it is to be understood that various modifications thereof
will become apparent to those skilled in the art upon reading the
specification. Therefore, it is to be understood that the invention
disclosed herein includes any such modifications that may fall within the
scope of the appended claims.

Patent applications by Georgeta Hategan, Plainfield, IL US

Patent applications by Stephen Augustine Dibiase, River Forest, IL US

Patent applications by Syed Q.a. Rizvi, Painesville, OH US

Patent applications in class The inorganic compound is a metal hydroxide or metal oxide

Patent applications in all subclasses The inorganic compound is a metal hydroxide or metal oxide